Method for improving fastness properties of fluorescent compounds on hair

ABSTRACT

Described herein is a method of treating the hair. The method includes applying to the hair a hair treatment composition including one or more fluorescent compounds and rinsing the hair with water. The one or more fluorescent compounds each include a fluorophore, one or two permanent cations, and one to four incipient cations. The incipient cations are pendant to the core structure and are neutral. The one or more fluorescent compounds enter the hair shaft after the hair treatment composition is applied to the hair. The hair treatment composition has a pH of from about 7 to about 11. The pH of the hair after rinsing is from about 3.5 to about 6. The rinsing of the hair causes one or more of the one to four incipient cations to change from neutral to positively charged inside of the hair shaft.

FIELD OF THE INVENTION

Provided is a method of treating hair with one or more washfastfluorescent compounds. The fluorescent compounds each have one to twopermanent positive charges and one to four incipient cations. A decreasein pH when rinsing the hair causes one or more of the incipient cationsto change from neutral to positively charged inside of the hair shaft,making them more resistant to water and shampoo.

BACKGROUND OF THE INVENTION

The unique physical properties of fluorophores allow them to provideoptical effects on hair that cannot be matched by typical dyes. Forexample, the appearance of lightening for dark hair can be offered byoptical brighteners. Brassiness in bleached hair can be minimized byfluorescent materials that emit green light which cancels the redcomponents in brassy hair. Fashion shades that are only visible underblack light can be achieved with fluorophores that absorb UV but emitvisible light. Fluorophores provide many desirable effects on hair thatcannot be provided by direct dyes and oxidative dyes alike.Understanding the factors contributing to washfastness would allow us tofind ways to enhance the washfastness properties of fluorescentmaterials.

The alteration of the appearance of keratinous fibers, in particularhuman hair, by the application of fluorophores has not yet become acommon practice in the salon or consumer's homes. However, the number ofpatent applications and granted patents in this particular field isabundant. According to these publications, applying fluorophores beendone mostly with anionic, cationic or zwitterionic fluorescentmaterials. In some cases, a mercapto group is attached to thefluorophore via a pendant group to allow the fluorescent material to becovalently bonded to keratin proteins to enhance the washfastness of thefluorophore. In some other cases, two fluorophores, typically identical,are linked together by a tethering group to produce a polycationicdimer. The challenge is to still meet all of the other requirements formaterials that improve the appearance of hair (e.g., little or nobleeding from the hair when it is wet, evenness, etc.)

We have learned that there are drawbacks in each one of the aboveapproaches to provide consumers an easy and pleasant experience. Anionicand zwitterionic fluorophores are not washfast as they constantly bleedout of hair fibers. Cationic fluorophores are better than anionic andzwitterionic counterparts in bleeding and washfastness, but they wouldstill fade with repetitive use of shampoo for hair cleansing. Theapproach through covalent bonding via disulfide bonds (reactivefluorophores) does not differentiate proteins in hair from skin.Dimerization of the fluorophores would increase the number of bindingsites that minimizes bleeding and loss caused by rinsing by providingstronger hair-fluorophore interactions. However, the same strong bindingforce to the cuticle also prevents the fluorophores from penetratingdeep into the cortex of hair, because it is difficult for fluorophoreswith multiple positive charges to diffuse through negatively chargednetworks of keratin proteins. Additionally, since polycationicfluorophores remain bound to the hair surface rather than penetratinginto the fiber, it is difficult to produce intense effects due tolimited binding sites on the surface of hair. The fluorophores wouldalso be at least twice as big as the monomer, which can become anotherobstacle for penetration.

SUMMARY OF THE INVENTION

Described herein is a method of imparting improved washfastness whentreating the hair with fluorescent compounds, the method comprising (a)applying to the hair a hair treatment composition comprising one or morefluorescent compounds, the one or more fluorescent compounds eachcomprising (i) a fluorophore; (ii) one or two permanent cations, whereinthe permanent cations are pendant to the fluorophore or part of thefluorophore, and wherein the fluorophore and the permanent cations forma core structure; (iii) one to four incipient cations, wherein theincipient cations are pendant to the core structure, and wherein theincipient cations are neutral; wherein the one or more fluorescentcompounds enter the hair shaft after the composition is applied to thehair; and wherein the hair treatment composition has a pH of from about7 to about 11; (b) rinsing the hair with water; wherein the pH of thehair after rinsing is from about 3.5 to about 6; and wherein the rinsingof the hair causes one or more of the one to four incipient cations tochange from neutral to positively charged inside of the hair shaft.

DETAILED DESCRIPTION OF THE INVENTION

While the specification concludes with claims which particularly pointout and distinctly claim the invention, it is believed the presentinvention will be better understood from the following description.

All percentages, parts and ratios are based upon the total weight of thecompositions of the present invention, unless otherwise specified. Allsuch weights as they pertain to listed ingredients are based on theactive level and, therefore, do not include solvents or by-products thatmay be included in commercially available materials, unless otherwisespecified. When more than one composition is used during a treatment, asin mixing of the components of a typical oxidative dye product, thetotal weight to be considered is the total weight of all thecompositions applied on the hair simultaneously (i.e. the weight found“on head”) unless otherwise specified. The term “weight percent” may bedenoted as “wt. %” herein.

As used herein, the term “hair” to be treated may be “living” i.e. on aliving body or may be “non-living” i.e. in a wig, hairpiece or otheraggregation of non-living keratinous fibers. Mammalian, particularlyhuman, hair is preferred. However, wool, fur, and other keratincontaining fibers are suitable substrates for the compositions accordingto the present invention.

As used herein, the term “pendant group” means a group of atoms attachedto the core structure or fluorophore. As described herein, the pendantgroup itself is not a fluorophore, although it may influence theemission spectrum of the fluorophore. The pendant group may be furtherclassified as an anchoring group or a hydrophobic group. A hydrophobicgroup (hydrophobe) is typically a carbon chain. An anchoring group is agroup attached to either a permanent cation or incipient cation,occasionally it is attached to both a permanent cation and one or moreincipient cations.

As used herein, the term “fluorophore” means the part of the fluorescentcompound responsible for providing the optical effect.

As used herein, the term “fluorescent compound” means a fluorescentmaterial used in a process in which fluorescent molecules are attractedby physical forces at the molecular level to a textile or substrate suchas the hair. As opposed to reactive fluorescent materials, there is nocovalent bond formation between the fluorescent compound and thesubstrate. The fluorescent compound does not undergo a chemicaltransformation before and after the treatment process.

As used herein, the term “core structure” means the fluorophoreincluding one or two permanent cations that are pendant to thefluorophore or part of the fluorophore. In an embodiment, thefluorophore is charged. In an embodiment, the fluorophore is not chargedas the permanent cation is pendant to the fluorophore.

As used herein, the term “pendant” means when a functional group islinked to a core structure via covalent bond.

As used herein, the term “incipient cation” means a functional groupthat goes from neutral to positively charged due to protonation during achange in pH.

As used herein, the term “non-anionic foaming agent” is a material thatfacilitates formation of foam. The term typically refers to a surfactantwhich, when present in small amounts, reduces the surface tension of aliquid or increases its colloidal stability by inhibiting coalescence ofbubbles.

As used herein, the term “hydrophobic moieties” means either hydrophobicmolecules or hydrophobic functional groups.

The hair brightening compositions of the present invention comprise oneor more washfast fluorescent compounds, optionally, direct dyes andoxidative dyes as well.

With regards to the fluorescent compounds described herein, numeroustautomeric compounds may be involved. Thus, for example,2-mercaptopyridine (I) may exist under known conditions in thepyridine-2-thione tautomer form (II).

It is to be understood that when this development refers to a particularstructure, all of the reasonable additional tautomeric structures areincluded. In the art, tautomeric structures are frequently representedby one single structure and the method described herein follows thisgeneral practice.

It is also understood that within the scope of this invention, E, Zisomers may be involved. Thus, for example, (E)-diphenyldiazene (III)converts under known conditions to (Z)-diphenyldiazene (IV), which isalso reversible.

It is to be understood that when this development refers to a particularstructure, all of the reasonable additional E, Z isomers are included.

I. Washfast Fluorescent Compounds

This invention relates to a novel approach where an incipient cation,typically an amino group or groups, is attached to the fluorophore inaddition to the existing permanent cation(s) to overcome the problemsencountered in previous attempts to make fluorescent materials morewashfast. The fluorophore would typically carry only one or twopermanent positive charges such as quaternary ammonium salts,pyridinium, imidazolium, thiazolium, oxazolium, triazolium,pyrimidinium, triazinium, tetrazolium phenoxazinium, phenazinium or ananalogous cation under basic conditions for typical hair treatmentapplications. The amino group(s) would remain mostly neutral under theapplication conditions (pH 10˜11) because the typical pK_(a) ofaliphatic amines falls between 9˜10.5. The fluorophore would carry onlyone or two cationic charges under such conditions, which provides theneeded affinity (Coulombic attraction) for optimized uptake withoutpreventing penetration due to relatively low charge density and smallersize compared to polycationic fluorophores. However, once theapplication is done and hair is rinsed, pH inside hair drops back to itsnatural pH, which is weakly acidic, the amino group(s) attached to thefluorophore would be protonated to become an ammonium cation, which addsone or more binding sites to the fluorophore. The pH change functions asa convenient switch to turn on additional binding group(s) to make thefluorophores more washfast. Primary amines work the best when comparedto secondary and tertiary amines for the following two reasons: 1.primary amines resist oxidation by hydrogen peroxide, while secondaryand tertiary amines can be oxidized and lose their anchoring capabilitywhen used together with a bleaching agent; 2. the protonated primaryammonium cation is the smallest in size, which allows strongerinteraction with anions in hair compared to secondary and tertiaryamines with more steric hindrance. However, in applications without anyoxidant, using secondary and tertiary amines as anchoring group wouldnot be a problem.

In short, the said inventive technology minimizes the number of positivecharges carried by the fluorophores under application conditions at highpH to facilitate penetration and deposition. After rinsing, however, theinventive technology maximizes the number of positive charges carried bythe fluorophores at hair's natural pH to provide the desirablewashfastness.

The linker groups, typically linear alkyl groups, would also function asmodulators for the overall hydrophobicity of the fluorophore. One of thecommon drawbacks of using combinations of cationic fluorophores isfading shift in the emission spectrum as different fluorophores would bewashed off hair at different rates, causing undesirable gradual shift influorescence over time.

Our technical approach minimizes this undesirable effect byincorporating identical charge patterns with similar overallhydrophobicity into different fluorophores to impart similar andenhanced washfastness profiles, so these inventive fluorophores are farmore washfast than typical cationic fluorophores. The inventivefluorophores exhibit minimal loss of the effect, while maintaining theoriginally imparted emission spectrum and optical effects. The inventivecompounds are substituted with one to two permanent cationic charges,preferably one, and one to four, preferably one or two, terminal aminogroups and derivatives thereof, according to the following formula:

-   -   i. a fluorophore;    -   ii. one or two permanent cations, wherein the permanent cations        are pendant to the fluorophore or part of the fluorophore, and        wherein the fluorophore and the permanent cations form a core        structure; and    -   iii. one to four incipient cations, wherein the one to four        incipient cations are pendant to the core structure, and wherein        the incipient cations are neutral at high pH.

The Markush structures of the inventive fluorescent materials can berepresented in the following ways, but not limited to what is shownbelow:(L₂)_(y)-F*(-L₁-A)_(n)  (XXI)(A₁-L₁-)_(n)F*(-L₂-A₂)_(m)(L₃)_(y)  (XXII)(Q*-L₃-)_(x)F(-L₁-A₁)_(m)(-L₂-A₂)_(n)(L₄)_(y)  (XXIII)(L₃)_(y)-F(-L₁-Q*(-L₂-A)_(m))_(n)  (XXIV)(L₂)_(y)-F*(-L₁-A₁(L₃-A₂)_(m))_(n)  (XXV)wherein

F is a fluorophore;

Q* is an organic cation;

* stands for a permanent cationic charge, it can also be part of afluorophore bearing a cationic charge;

L is a linker or hydrophobic chain and;

A is the anchoring group, the fastness enhancer. It is typically aprimary, secondary or tertiary amino group, preferably a primary amine.It is also a switch to allow the anchor to go between neutral andcharged states when the pH in the surrounding environment changes.

n=1˜4; m=1˜4; n+m≦4; x=1˜2; y=0˜2.

In some embodiments, F is of formula XXVIa

wherein

G is an alkenyl, polyalkenyl chain or aromatic ring system thatconjugates the two benzoxazole moieties. G can be —(CH═CH)_(n)— withn=1˜5, p-phenylene or 1,1′-biphenyl; and

R_(1a), R_(1b), R_(1c), R_(1d), R_(1e), R_(1f), R_(1g) and R_(1h) areeach independently hydrogen, alkyl, halogen substituted alkyl, alkenyl,alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro,nitroso, cyano, a heterocyclic moiety, thioether; linker group L orlinker group L with a primary, secondary or tertiary amino groupattached; and

At least one of R_(1a), R_(1b), R_(1c), R_(1d), R_(1e), R_(1f), R_(1g)and R_(1h) must be linker group L with a cationic moiety attached to it.The cationic group is a quaternary ammonium, imidazolium, pyridinium,oxazolium or thiazolium. It can also take on the following form asL₁-Q*(-L₂A)_(n), where L₁ and L₂ can be the same or different, Q* is thecationic moiety, A is an amino group; and n is either 1 or 2; and

The total number of permanent cationic charge among R_(1a), R_(1b),R_(1c), R_(1d), R_(1e), R_(1f), R_(1g) and R_(1h) is 1 or 2; the totalnumber of amino groups among R_(1a), R_(1b), R_(1c), R_(1d), R_(1e),R_(1f), R_(1g) and R_(1h) is 1-4; the amino group can be primary,secondary or tertiary; and cosmetically acceptable salt thereof.

In some embodiments, L is of formula (XXVII)

wherein

L is covalently linked to the fluorophore F of formula (XXVIa); L can belinked to F either by its left-hand or right-hand side.

a, c, e and g are each independently an integer from 0-3, provided thatthe sum of a, c, e and g is greater than or equal to 2; b, d and f areeach independently either 0 or 1; R₅₀, R₅₁, R₅₂, R₅₃, R₅₄, R₅₅, R₅₆ andR₅₇ are each independently hydrogen or C₁-C₂ alkyl group;

U is an aromatic ring, alkenyl or alkynyl moiety;

V is a hetero atom O, N or S;

W is a cyclic aliphatic ring.

In other embodiments, the fluorophore F is of formula (XXVIb);

wherein

X can be NR_(2f)R_(2g), OR_(2h) or SR_(2i).

R_(2a), R_(2b), R_(2c), R_(2d) and R_(2e) are each independentlyhydrogen, alkyl, halogen substituted alkyl, alkenyl, alkynyl, aryl,hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro, nitroso, cyano, aheterocyclic moiety, thioether; linker group L or linker group L with aprimary, secondary or tertiary amino group attached; and

R_(2f), R_(2g), R_(2h) and R_(2i) are each independently hydrogen,alkyl, substituted alkyl, aryl, a heterocyclic moiety, linker group L orlinker group L with a primary, secondary or tertiary amino groupattached; and

One of R_(2a), R_(2b), R_(2c), R_(2d), R_(2e), R_(2f), R_(2g), R_(2h)and R_(2i) must be linker group L with a cationic moiety attached to it.The cationic group is a quaternary ammonium, imidazolium, pyridinium,oxazolium or thiazolium. It can also take on the following form asL₁-Q*(-L₂A)_(n), where L₁ and L₂ can be the same or different, Q* is thecationic moiety, A is an amino group; and n is either 1 or 2; and

The total number of permanent cationic charge among R_(2a), R_(2b),R_(2c), R_(2d), R_(2e), R_(2f), R_(2g), R_(2h) and R_(2i) is 1 or 2; thetotal number of amino groups among R_(2a), R_(2b), R_(2e), R_(2d),R_(2e), R_(2f), R_(2g), R_(2h) and R_(2i), is 1-4; the amino group canbe primary, secondary or tertiary; and cosmetically acceptable saltthereof.

In other embodiments, the fluorophore F is of formula (XXVIc);

wherein

R_(3b), R_(3c), R_(3d), R_(3e), R_(3f), R_(3g), R_(3i), R_(3j), R_(3k),R_(3l), R_(3m) and R_(3n) are each independently hydrogen, alkyl,halogen substituted alkyl, alkenyl, alkynyl, aryl, hydroxyl alkyl,alkoxy, aryloxy, acyl, halogen, nitro, nitroso, cyano, a heterocyclicmoiety, thioether or are attached to linker L with or without a terminalamino group; and

R_(3a) and R_(3h) are linker group L with a primary, secondary ortertiary amino group attached;

The total number of amino groups attached to R_(3a), R_(3h) is 1 or 2;the amino group can be primary, secondary or tertiary; and cosmeticallyacceptable salt thereof.

In other embodiments, the fluorophore F is of formula (XXVId);

wherein

R_(4a), R_(4b), R_(4e), R_(4f), R_(4i), R_(4j), R_(4k) are eachindependently hydrogen, alkyl, halogen substituted alkyl, alkenyl,alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro,nitroso, cyano, a heterocyclic moiety, thioether or are attached tolinker L with or without a terminal amino group; and

R_(4c), R_(4d), R_(4g) and R_(4h) are each independently hydrogen, C₁-C₈alkyl or linker group L with a primary, secondary or tertiary aminogroup attached. At least one of R_(4c), R_(4d), R_(4g) and R_(4h) mustbe linker group L with a cationic moiety attached to it. The cationicgroup is a quaternary ammonium, imidazolium, pyridinium, oxazolium orthiazolium. It can also take on the following form as L₁-Q*(-L₂A)_(n),where L₁ and L₂ can be the same or different, Q* is the cationic moiety,A is an amino group; and n is either 1 or 2; and

The total number of permanent cationic charge among R_(4c), R_(4d),R_(4g) and R_(4h) is 1 or 2; the total number of amino groups amongR_(4c), R_(4d), R_(4g) and R_(4h) is 1, 2, 3 or 4; the amino group canbe primary, secondary or tertiary; and cosmetically acceptable saltthereof.

In other embodiments, the fluorophore F is of formula (XXVIe);

wherein

R_(5a), R_(5b), R_(5c), R_(5h), R_(5k) and R_(5l) are each independentlyhydrogen, alkyl, halogen substituted alkyl, alkenyl, alkynyl, aryl,hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro, nitroso, cyano, aheterocyclic moiety, thioether or are attached to linker L; and

R_(5g) is an aryl group which can be substituted or unsubstitutedphenyl, naphthyl, pyridinyl, pyrimidinyl, triazinyl, thienyl, thiazolyl,imidazolyl, oxazolyl or indolyl; and

R_(5f) is linker group L with a primary, secondary or tertiary aminogroup attached; and

R_(5c), R_(5d), R_(5i) and R_(5j) are each independently hydrogen, C₁-C₈alkyl or linker group L with a primary, secondary or tertiary aminogroup attached; and

The total number of amino groups among R_(5c), R_(5d), R_(5f), R_(5i)and R_(5j) is 1, 2, 3, or 4; the amino group can be primary, secondaryor tertiary; and cosmetically acceptable salt thereof.

In other embodiments, the fluorophore F is of formula (XXVIf);

wherein

R_(6b), R_(6c), R_(6d), R_(6e), R_(6f), R_(6g), R_(6h), R_(6j) andR_(6k) are each independently hydrogen, alkyl, halogen substitutedalkyl, alkenyl, alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl,halogen, nitro, nitroso, cyano, a heterocyclic moiety, thioether or areattached to linker L; and

R_(6a) and R_(6i) are each independently, C₁-C₈ alkyl or linker group Lwith a primary, secondary or tertiary amino group attached; and

The total number of amino groups in R_(6a) and R_(6i) is 1 or 2; aminogroup can be primary, secondary or tertiary; and cosmetically acceptablesalt thereof.

In other embodiments, the fluorophore F is of formula (XXVIg);

wherein

R_(7b), R_(7c), R_(7d), R_(7e), R_(7f), R_(7g), R_(7i), R_(7j) R_(7k),R_(7l) and R_(7m) are each independently hydrogen, alkyl, halogensubstituted alkyl, alkenyl, alkynyl, aryl, hydroxyl alkyl, alkoxy,aryloxy, acyl, halogen, nitro, nitroso, cyano, a heterocyclic moiety,thioether or are attached to linker L; and

R_(7a) and R_(7h) are each independently, C₁-C₈ alkyl or linker group Lwith a primary, secondary or tertiary amino group attached; and

The total number of amino groups in R_(7a) and R_(7h) is 1 or 2; aminogroup can be primary, secondary or tertiary; and cosmetically acceptablesalt thereof.

In other embodiments, the fluorophore F is of formula (XXVIh);

wherein

R_(8b) and R_(8c) are halogen, hydrogen, alkyl, halogen substitutedalkyl or cyano; and

R_(8a), R_(8d) and R_(8e) are each independently hydrogen, C₁-C₈ alkylor linker group L with a primary, secondary or tertiary amino groupattached. At least one of R_(8a), R_(8d) and R_(8e) must be linker groupL with a cationic moiety attached to it. The cationic group is aquaternary ammonium, imidazolium, pyridinium, oxazolium or thiazolium.It can also take on the following form as L₁-Q*(-L₂A)_(n), where L₁ andL₂ can be the same or different, Q* is the cationic moiety, A is anamino group; and n is either 1 or 2; and

The total number of permanent cationic charge among R_(8a), R_(8d) andR_(8e) is 1 or 2; the total number of amino groups among R_(4c), R_(4d),R_(4g) and R_(4h) is 1, 2, 3 or 4; the amino group can be primary,secondary or tertiary; and cosmetically acceptable salt thereof.

In other embodiments, the fluorophore F is of formula (XXVIi);

wherein

R_(9c) and R_(9d) are each independently hydrogen, alkyl, halogensubstituted alkyl, alkenyl, alkynyl, aryl, hydroxyl alkyl, alkoxy,aryloxy, acyl, halogen, nitro, nitroso, cyano, a heterocyclic moiety,thioether or are attached to linker L; and

R_(9a) and R_(9b) are each independently hydrogen, C₁-C₈ alkyl or linkergroup L with a primary, secondary or tertiary amino group attached. Atleast one of R_(9a) and R_(9b) must be linker group L with a cationicmoiety attached to it. The cationic group is a quaternary ammonium,imidazolium, pyridinium, oxazolium or thiazolium. It can also take onthe following form as L₁-Q*(-L₂A)_(n), where L₁ and L₂ can be the sameor different, Q* is the cationic moiety, A is an amino group; and n iseither 1 or 2; and

The total number of permanent cationic charge in R_(9a) and R_(9b) is 1or 2; the total number of amino groups in R_(9a) and R_(9b) is 1, 2, 3or 4; the amino group can be primary, secondary or tertiary; andcosmetically acceptable salt thereof.

In other embodiments, the fluorophore F is of formula (XXVIj);

wherein

R_(10b), R_(10c), R_(10d), R_(10e), R_(10h), R_(10i), R_(10j) andR_(10k) are each independently hydrogen, alkyl, halogen substitutedalkyl, alkenyl, alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl,halogen, nitro, nitroso, cyano, a heterocyclic moiety, thioether or areattached to linker L; and

R_(10a), R_(10f) and R_(10g) are each independently, C₁-C₈ alkyl orlinker group L with a primary, secondary or tertiary amino groupattached; and

The total number of amino groups in R_(10a), R_(10f) and R_(10g) is 1 to3; amino group can be primary, secondary or tertiary; and cosmeticallyacceptable salt thereof.

In other embodiments, the fluorophore F is of formula (XXVIk);

wherein

R_(11b), R_(11c), R_(11d), R_(11e), R_(11f), R_(11g), R_(11j) andR_(11k) are each independently hydrogen, alkyl, halogen substitutedalkyl, alkenyl, alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl,halogen, nitro, nitroso, cyano, a heterocyclic moiety, thioether or areattached to linker L; and

R_(11a), R_(11h) and R_(11i) are each independently, C₁-C₈ alkyl orlinker group L with a primary, secondary or tertiary amino groupattached; and

The total number of amino groups in R_(11a), R_(11h) and R_(11i) is 1 to3; amino group can be primary, secondary or tertiary; and cosmeticallyacceptable salt thereof.

In other embodiments, the fluorophore F is of formula (XXVII);

wherein

R_(12c), R_(12d), R_(12g) and R_(12h) are each independently hydrogen,alkyl, halogen substituted alkyl, alkenyl, alkynyl, aryl, hydroxylalkyl, alkoxy, aryloxy, acyl, halogen, nitro, nitroso, cyano, aheterocyclic moiety, thioether or are attached to linker L; and

R_(12a), R_(12b), R_(12e) and R_(12f) are each independently, C₁-C₈alkyl or linker group L with a primary, secondary or tertiary aminogroup attached; and

The total number of amino groups in R_(12a), R_(12b), R_(12e) andR_(12f) is 1 to 4; amino group can be primary, secondary or tertiary;and cosmetically acceptable salt thereof.

In other embodiments, the fluorophore F is of formula (XXVIm);

wherein

R_(13c), R_(13d), R_(13f), R_(13g), R_(13h), R_(13i), and R_(13k) areeach independently hydrogen, alkyl, halogen substituted alkyl, alkenyl,alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro,nitroso, cyano, a heterocyclic moiety, thioether or are attached tolinker L; and

R_(13a), R_(13b), R_(13e) and R_(13j) are each independently, C₁-C₈alkyl or linker group L with a primary, secondary or tertiary aminogroup attached; and

The total number of amino groups in R_(13a), R_(13b), R_(13e) andR_(13j) is 1 to 4; amino group can be primary, secondary or tertiary;and cosmetically acceptable salt thereof.

In other embodiments, the fluorophore F is of formula (XXVIn);

wherein

R_(14a), R_(14d), R_(14e), R_(14f), R_(14g) and R_(13ih) are eachindependently hydrogen, alkyl, halogen substituted alkyl, alkenyl,alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro,nitroso, cyano, a heterocyclic moiety, thioether or are attached tolinker L; and

R_(14b) and R_(14c) are each independently, hydrogen, C₁-C₈ alkyl orlinker group L with a primary, secondary or tertiary amino groupattached. At least one of R_(14b) and R_(14c) must be linker group Lwith a cationic moiety attached to it. The cationic group is aquaternary ammonium, imidazolium, pyridinium, oxazolium or thiazolium.It can also take on the following form as L₁-Q*(-L2A)_(n), where L₁ andL₂ can be the same or different, Q* is the cationic moiety, A is anamino group; and n is either 1 or 2; and

The total number of amino groups in R_(14b) and R_(14c) is 1 to 4; aminogroup can be primary, secondary or tertiary; and cosmetically acceptablesalt thereof.

In other embodiments, the fluorophore F is of formula (XXVIo);

wherein

R_(15a), R_(15b), R_(15c), R_(15d), R_(15e) and R_(15f) are eachindependently hydrogen, alkyl, halogen substituted alkyl, alkenyl,alkynyl, aryl, hydroxyl alkyl, alkoxy, aryloxy, acyl, halogen, nitro,nitroso, cyano, a heterocyclic moiety, thioether or are attached tolinker L; and

R_(15a), R_(15b), R_(15c), R_(15d), R_(15e) and R_(15f) can also be eachindependently, C₁-C₈ alkyl or linker group L with a primary, secondaryor tertiary amino group attached; and

At least one of R_(15a), R_(15b), R_(15c), R_(15d), R_(15e) and R_(15f)must be linker group L with a cationic moiety attached to it. Thecationic group is a quaternary ammonium, imidazolium, pyridinium,oxazolium or thiazolium. It can also take on the following form asL₁-Q*(-L₂A)_(n), where L₁ and L₂ can be the same or different, Q* is thecationic moiety, A is an amino group; and n is either 1 or 2; and

The total number of amino groups in R_(15a), R_(15b), R_(15c), R_(15d),R_(15e) and R_(15f) is 1 to 4; amino group can be primary, secondary ortertiary; and cosmetically acceptable salt thereof.

Example 1

In example 1, the permanent charge is part of the fluorophore andresides on the indolium moiety. The incipient cations are linked to thefluorophore via propylene groups.

Neat 2,3,3-trimethylindolenine (1.6 g) and 3-(Boc-amino)propyl bromide(2.4 g, 1.0 eq.) were mixed, magnetically stirred and heated to 100° C.for 3 hours. After cooling, triethoxymethane (0.74 g, 0.5 eq.) andpyridine (50 ml) were added to the reaction flask. The reaction mixturewas refluxed for 3 hours, after which pyridine was evaporated in vacuo.The desired violet fluorescent compound was purified on preparative HPLCwith C18 reverse phase column and water/methanol (with 0.1% TFA) asmobile phase. The final product (XXVIII) was obtained after Boc groupwas removed by ethanolic HCl followed by evaporation. ¹H NMR: (600.1MHz, DMSO-d₆) δ=1.73 (12H, s), 2.02-2.07 (4H, m), 2.94-2.97 (4H, m),4.21 (4H, br t), 6.50 (2H, d, J=13.6 Hz), 7.33-7.36 (2H, m), 7.47-7.50(2H, m), 7.53 (2H, d, J=8.0 Hz), 7.67-7.72 (8H, m), 8.40 (1H, t, J=13.6Hz); ¹³C NMR: (150.9 MHz, DMSO-d₆) δ=25.12, 27.32, 36.38, 41.96, 48.92,102.33, 111.31, 122.52, 125.35, 128.51, 140.51, 141.62, 150.15, 174.23.

Example 2

In example 2, the permanent charge is part of the fluorophore thatresides on the pyridinium moiety. The incipient cations are linked tothe fluorophore via propylene groups.

Nicotinaldehyde (1.07 g) was mixed with 2-hydrazinylbenzo[d]thiazole(1.0 eq., 1.65 g) in DMSO (15 mL) and stirred magnetically overnight.The resulting pale yellow slurry was dumped into ice-water and thenfiltered. The yellow cake collected from filtration is the desiredintermediate. A portion of the intermediate,(Z)-2-(((E)-pyridin-3-ylmethylene)hydrazono)-2,3-dihydrobenzo[d]thiazole(0.5 g), was dissolved in DMF (15 mL) and reacted with3-((t-butoxycarbonyl)amino)propyl bromide (2.1 eq.) and sodiumbicarbonate (1.5 eq.). The reaction mixture was heated to 80° C. andmagnetically stirred overnight. After the bisalkylation was complete,the Boc protection group was removed by adding concentrated aqueous HClsolution to the crude reaction mixture. DMF and water was then removedunder vacuum. The resulting crude reaction mixture was purified onpreparative reverse phase HPLC with water/methanol (with 0.1% TFA) asmobile phase. The final product (XXIX) was collected as itscorresponding trifluoroacetate salt.

Exemplary Formulations

% by weight Composition A Washfast Fluorescent Compound 0.50 AmmoniumHydroxide (aq. 28% active) 4.50 Water 95.00 Composition B WashfastFluorescent Compound 0.50 Ammonium carbonate 10.00 Water 89.50Composition C Washfast Fluorescent Compound 0.50 FlexiThix ™ 5.00Phenoxyethanol 0.30 Sodium Benzoate 0.30 Disodium EDTA 0.10 AmmoniumHydroxide (aq. 28% active) 4.00 Water 89.80 Composition D WashfastFluorescent Compound 0.50 Aculyn ™ 46 15.80 Phenoxyethanol 0.30 SodiumBenzoate 0.30 Disodium EDTA 0.10 Ammonium Hydroxide (aq. 28% active)4.00 Water 79.00 Composition E Washfast Fluorescent Compound 0.50Plantaren ® 2000 N UP 20.00 Phenoxyethanol 0.30 Sodium Benzoate 0.30Disodium EDTA 0.10 Ammonium Hydroxide (aq. 28% active) 4.00 Water 74.80Composition F Washfast Fluorescent Compound 0.50 Non-anionic foamingagent 5.00 Phenoxyethanol 0.30 Sodium Benzoate 0.30 Disodium EDTA 0.10Ammonium Hydroxide (aq. 28% active) 4.00 Water 89.80

The compositions of the invention may be formed as thick liquid, cream,gel, emulsion, foam, aerosol mousse or as a solid form to which water isadded to generate the oxidant and form a thickened vehicle suitable forhair treatment. They may comprise in addition to the ingredientsindicated above further ingredients in order to further enhance theproperties of the composition, including but not limited to: solvents;oxidative dyes, direct dyes; oxidizing agents; radical scavengers;thickeners and or rheology modifiers; chelants; pH modifiers andbuffering agents; carbonate ion sources; peroxymonocarbonate ionsources; anionic, cationic, nonionic, amphoteric or zwitterionicsurfactants, or mixtures thereof; anionic, cationic, nonionic,amphoteric or zwitterionic polymers, or mixtures thereof; fragrances;enzymes; dispersing agents; peroxide stabilizing agents; antioxidants;natural ingredients, e.g. proteins and protein compounds, and plantextracts; conditioning agents including silicones and cationic polymers,ceramides, preserving agents; and opacifiers and pearling agents (suchas titanium dioxide and mica). Some adjuvants referred to above, but notspecifically described below, which are suitable are listed in theInternational Cosmetics Ingredient Dictionary and Handbook, (8th ed.;The Cosmetics, Toiletry, and Fragrance Association). Particularly, vol.2, sections 3 (Chemical Classes) and 4 (Functions) are useful inidentifying specific adjuvants to achieve a particular purpose ormultipurpose. A few of these ingredients are discussed hereinbelow,whose disclosure is of course non-exhaustive.

Other Ingredients

The composition according to the present invention may comprise, inaddition to the ingredients indicated above, further ingredients inorder to further enhance the properties of the composition, as long asthese are not excluded by the claims.

Suitable further ingredients include, but not limited to: solvents;oxidizing agents; alkalizing agents; oxidative dye precursors, directdyes; chelants; radical scavengers; pH modifiers and buffering agents;thickeners and/or rheology modifiers; carbonate ion sources;peroxymonocarbonate ion sources; anionic, cationic, nonionic, amphotericor zwitterionic surfactants, and mixtures thereof; anionic, cationic,nonionic, amphoteric or zwitterionic polymers, and mixtures thereof;fragrances; enzymes; dispersing agents; peroxide stabilizing agents;antioxidants; natural ingredients (such as proteins, protein compounds,and plant extracts); conditioning agents (such as silicones and cationicpolymers); ceramides; preserving agents; opacifiers and pearling agents(such as titanium dioxide and mica); and mixtures thereof. Suitablefurther ingredients referred to above, but not specifically describedbelow, are listed in the International Cosmetics Ingredient Dictionaryand Handbook, (8th ed.; The Cosmetics, Toiletry, and FragranceAssociation). Particularly, vol. 2, sections 3 (Chemical Classes) and 4(Functions), which are useful in identifying specific adjuvants toachieve a particular purpose or multipurpose. A few of these ingredientsare discussed hereinbelow, whose disclosure is of course non-exhaustive.

Solvents

The composition according to the present invention may further comprisea solvent. The solvent may be selected from water, or a mixture of waterand at least one organic solvent to dissolve the compounds that wouldnot typically be sufficiently soluble in water.

Suitable organic solvents include, but are not limited to: C1 to C4lower alkanols (such as ethanol, propanol, isopropanol); aromaticalcohols (such as benzyl alcohol and phenoxyethanol); polyols and polyolethers (such as carbitols, 2-butoxyethanol, propylene glycol, propyleneglycol monomethyl ether, diethylene glycol monoethyl ether, monomethylether, hexylene glycol, glycerol, ethoxy glycol, butoxydiglycol,ethoxydiglycerol, dipropyleneglocol, polygylcerol); propylene carbonate;and mixtures thereof.

In one embodiment, the solvent may be selected from the group consistingof water, ethanol, propanol, isopropanol, glycerol, 1,2-propyleneglycol, hexylene glycol, ethoxy diglycol, and mixtures thereof.

Typically, the composition may comprise water as a main ingredient,particularly in a total amount ranging from at least about 50%,alternatively from at least about 60%, alternatively from at least about70%, by weight of the total composition. Typically, when present, thecomposition comprises a total amount of organic solvents ranging fromabout 1% to about 30%, by weight of the total composition.

Oxidizing Agent

The composition may comprise at least one source of an oxidizing agent.Preferred oxidizing agents for use herein are water soluble peroxygenoxidizing agents. Water-soluble peroxygen oxidizing agents are wellknown in the art and include, but are not limited to, hydrogen peroxide,inorganic alkali metal peroxides such as sodium periodate and sodiumperoxide and organic peroxides such as urea peroxide, melamine peroxide,and inorganic perhydrate salt bleaching compounds, such as the alkalimetal salts of perborates, percarbonates, perphosphates, persilicates,persulfates and the like. These inorganic perhydrate salts may beincorporated as monohydrates, tetrahydrates etc. Alkyl and arylperoxides, and or peroxidases, oxidases, and uricases and theirsubstrates may also be used. Mixtures of two or more such oxidizingagents can also be used if desired. The oxidizing agents may be providedin aqueous solution or as a powder which is dissolved prior to use.Preferred for use in the compositions are hydrogen peroxide,percarbonate, persulfates and combinations thereof.

In one embodiment, the composition comprises from 0.1% to 20% by weight,or from 1% to 15% by weight, or from 2% to 10% by weight of oxidizingagent.

A potential oxidizing agent for use herein is a source ofperoxymonocarbonate ions formed in situ from a source of hydrogenperoxide and a hydrogen carbonate ion source. Moreover, this system isalso particularly effective in combination with a source of ammonia orammonium ions. Accordingly, any source of these peroxymonocarbonate ionsmay be used. Suitable sources for use herein include sodium, potassium,guanidine, arginine, lithium, calcium, magnesium, barium, ammonium saltsof carbonate, carbamate and hydrocarbonate ions and mixtures thereofsuch as sodium carbonate, sodium hydrogen carbonate, potassiumcarbonate, potassium hydrogen carbonate, guanidine carbonate, guanidinehydrogen carbonate, lithium carbonate, calcium carbonate, magnesiumcarbonate, barium carbonate, ammonium carbonate, ammonium hydrogencarbonate and mixtures thereof. Percarbonate salts may be used both asan oxidizing agent and as a source of carbonate ions. Preferred sourcesof carbonate ions, carbamate and hydrocarbonate ions are sodium hydrogencarbonate, potassium hydrogen carbonate, ammonium carbamate, andmixtures thereof.

The oxidative agent may comprise from 0.1% to 15% by weight, or from 1%to 10% by weight, or from 1% to 8% by weight of a hydrogen carbonateion; and from 0.1% to 10% by weight, or from 1% to 7% by weight, or from2% to 5% by weight of the oxidative agent of a source of hydrogenperoxide.

Alkalizing Agent

The composition may further comprise, generally in the fluorophorecomponent, an alkalizing agent as known in the art. Any alkalizing agentknown in the art may be used such as ammonia, alkanolamines for examplemonoethanolamine, diethanolamine, triethanolamine, monopropanolamine,dipropanolamine, tripropanolamine, 2-amino-2-methyl-1,3-propanediol,2-amino-2-methyl-1-propanol, and2-amino-2-hydroxymethyl-1,3-propanediol, guanidium salts, alkali metaland ammonium hydroxides such as sodium hydroxide, alkali metal andammonium carbonates, and mixtures thereof. Typical alkalizing agents areammonia and/or monoethanolamine.

Typically, the compositions for the oxidative treatment of keratinfibers comprise from about 0.1% to about 10%, preferably from about 0.5%to about 6%, more preferably from about 1% to about 4% by weight of thealkalizing agent relative to the total weight of the composition.

The compositions described above may have a pH of from 7 to 12,preferably from 8 to 11. For embodiments comprising aperoxymonocarbonate ion, the pH is preferably up to and including pH9.5, more preferably from 7.5 to 9.5, even more preferably from 8.4 to9.5, most preferably from 8.5 to 9.4, for example, 9.0 or 9.3.

Any sub-components of the compositions, such as a fluorophorecomposition or an oxidizing composition, may have a different pH fromthe fluorophore composition. For example, if the fluorophore compositioncomprises an alkalizing agent, the fluorophore composition will have analkaline pH, such as higher than 7. The oxidizing composition maycomprise an acidic pH of less than 7.

When the composition of the present invention is obtained by mixing adeveloper and a fluorophore composition prior to use, the alkalizingagent is generally present in the fluorophore composition.

Oxidative Dye Precursors

In addition to the fluorophores of the invention, the compositionaccording to the present invention may further comprise oxidative dyeprecursors, which are usually classified either as primary intermediates(also known as developers) or couplers (also known as secondaryintermediates). Various couplers may be used with primary intermediatesin order to obtain different shades. Oxidative dye precursors may befree bases or the cosmetically acceptable salts thereof.

Typically, the composition may comprise a total amount of oxidative dyeprecursors ranging up to about 12%, alternatively from about 0.1% toabout 10%, alternatively from about 0.3% to about 8%, alternatively fromabout 0.5% to about 6%, by weight of the total composition. Suitableprimary intermediates include, but are not limited to:toluene-2,5-diamine, p-phenylenediamine, N-phenyl-p-phenylenediamine,N,N-bis(2-hydroxyethyl)-p-phenylenediamine,2-hydroxyethyl-p-phenylenediamine,hydroxypropyl-bis-(N-hydroxyethyl-p-phenylenediamine),2-methoxymethyl-p-phenylenediamine,2-(1,2-dihydroxyethyl)-p-phenylenediamine,2,2′-(4-aminophenylamino)ethylazanediyl)diethanol,2-(2,5-diamino-4-methoxyphenyl)propane-1,3-diol,2-(7-amino-2H-benzol[b][1,4]oxazin-4(3H)-yl)ethanol,2-chloro-p-phenylenediamine, p-aminophenol, p-(methylamino)phenol,4-amino-m-cresol, 6-amino-m-cresol, 5-ethyl-o-aminophenol,2-methoxy-p-phenylenediamine, 2,2′-methylenebis-4-aminophenol,2,4,5,6-tetraminopyrimidine, 2,5,6-triamino-4-pyrimidinol,1-hydroxyethyl-4,5-diaminopyrazole sulfate,4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole,4,5-diamino-1-isopropylpyrazole, 4,5-diamino-1-butylpyrazole,4,5-diamino-1-pentylpyrazole, 4,5-diamino-1-benzylpyrazole,(2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-onedimethanesulfonate), 4,5-diamino-1-hexylpyrazole,4,5-diamino-1-heptylpyrazole, methoxymethyl-1,4-diaminobenzene,N,N-bis(2-hydroxyethyl)-N-(4-aminophenyl)-1,2-diaminothane,2-[(3-aminopyrazolo[1,5-a]pyridin-2-yl)oxy]ethanol hydrochloride, saltsthereof and mixtures thereof.

Suitable couplers include, but are not limited to: resorcinol,4-chlororesorcinol, 2-chlororesorcinol, 2-methylresorcinol,4,6-dichlorobenzene-1,3-diol, 2,4-dimethylbenzene-1,3-diol,m-aminophenol, 4-amino-2-hydroxytoluene,2-methyl-5-hydroxyethylaminophenol, 3-amino-2,6-dimethylphenol,3-amino-2,4-dichlorophenol, 5-amino-6-chloro-o-cresol,5-amino-4-chloro-o-cresol, 6-hydroxybenzomorpholine,2-amino-5-ethylphenol, 2-amino-5-phenylphenol, 2-amino-5-methylphenol,2-amino-6-methylphenol, 2-amino-5-ethoxyphenol,5-methyl-2-(methylamino)phenol, 2,4-diaminophenoxyethanol,2-amino-4-hydroxyethylaminoanisole,1,3-bis-(2,4-diaminophenoxy)-propane,2,2′-(2-methyl-1,3-phenylene)bis(azanediyl)diethanol,benzene-1,3-diamine, 2,2′-(4,6-diamino-1,3-phenylene)bis(oxy)diethanol,3-(pyrrolidin-1-yl)aniline, 1-(3-(dimethylamino)phenyl)urea,1-(3-aminophenyl)urea, 1-naphthol, 2-methyl-1-naphthol,1,5-naphthalenediol, 2,7-naphthalenediol or1-acetoxy-2-methylnaphthalene, 4-chloro-2-methylnaphthalen-1-ol,4-methoxy-2-methylnaphthalen-1-ol, 2,6-dihydroxy-3,4-dimethylpyridine,2,6-dimethoxy-3,5-pyridinediamine,3-amino-2-methylamino-6-methoxypyridine, 2-amino-3-hydroxypyridine,2,6-diaminopyridine, pyridine-2,6-diol, 5,6-dihydroxyindole,6-hydroxyindole, 5,6-dihydroxyindoline,3-methyl-1-phenyl-1H-pyrazol-5(4H)-one, 1,2,4-trihydroxybenzene,2-(benzo[d][1,3]dioxol-5-ylamino)ethanol (also known ashydroxyethyl-3,4-methylenedioxyaniline), and mixtures thereof.

When the composition of the invention is obtained by mixing afluorophore composition and a developer composition, the primaryintermediates and couplers are usually incorporated into the fluorophorecomposition.

Direct Dyes

The composition according to the present invention may further comprisecompatible direct dyes, in an amount sufficient to provide additionalcoloring, particularly with regard to intensity. Typically, thecomposition may comprise a total amount of direct dyes ranging fromabout 0.05% to about 4%, by weight of the total composition.

Suitable direct dyes include but are not limited to: Acid dyes such asAcid Yellow 1, Acid Orange 3, Acid Black 1, Acid Black 52, Acid Orange7, Acid Red 33, Acid Yellow 23, Acid Blue 9, Acid Violet 43, HC Blue 16,Acid Blue 62, Acid Blue 25, Acid Red 4; Basic Dyes such as Basic Brown17, Basic Red 118, Basic Orange 69, Basic Red 76, Basic Brown 16, BasicYellow 57, Basic Violet 14, Basic Blue 7, Basic Blue 26, Basic Red 2,Basic Blue 99, Basic Yellow 29, Basic Red 51, Basic Orange 31, BasicYellow 87, Basic Blue 124,4-(3-(4-amino-9,10-dioxo-9,10-dihydroanthracen-1-ylamino)propyl)-4-methylmorpholin-4-ium-methylsulfate,(E)-1-(2-(4-(4,5-dimethylthiazol-2-yl)diazenyl)phenyl)(ethyl)amino)ethyl)-3-methyl-1H-imidazol-3-iumchloride,(E)-4-(2-(4-(dimethylamino)phenyediazenyl)-1-methyl-1H-imidazol-3-ium-3-yl)butane-1-sulfonate,(E)-4-(4-(2-methyl-2-phenylhydrazono)methyl)pyridinium-1-yl)butane-1-sulfonate,N,N-dimethyl-3-(4-(methylamino)-9,10-dioxo-4a,9,9a,10-tetrahydroanthracen-1-ylamino)-N-propylpropan-1-aminiumbromide; Disperse Dyes such as Disperse Red 17, Disperse Violet 1,Disperse Red 15, Disperse Black 9, Disperse Blue 3, Disperse Blue 23,Disperse Blue 377; Nitro Dyes such as1-(2-(4-nitrophenylamino)ethyl)urea,2-(4-methyl-2-nitrophenylamino)ethanol, 4-nitrobenzene-1,2-diamine,2-nitrobenzene-1,4-diamine, Picramic acid, HC Red No. 13,2,2′-(2-nitro-1,4-phenylene)bis(azanediyediethanol, HC Yellow No. 5, HCRed No. 7, HC Blue No. 2, HC Yellow No. 4, HC Yellow No. 2, HC OrangeNo. 1, HC Red No. 1, 2-(4-amino-2-chloro-5-nitrophenylamino)ethanol, HCRed No. 3, 4-amino-3-nitrophenol, 4-(2-hydroxyethylamino)-3-nitrophenol,2-amino-3-nitrophenol, 2-(3-(methylamino)-4-nitrophenoxy)ethanol,3-(3-amino-4-nitrophenyl)propane-1,2-diol, HC Yellow No. 11, HC VioletNo. 1, HC Orange No. 2, HC Orange No. 3, HC Yellow No. 9, HC Red No. 10,HC Red No. 11, 2-(2-hydroxyethylamino)-4,6-dinitrophenol, HC Blue No.12, HC Yellow No. 6, HC Yellow No. 12, HC Blue No. 10, HC Yellow No. 7,HC Yellow No. 10, HC Blue No. 9, 2-chloro-6-(ethylamino)-4-nitrophenol,6-nitropyridine-2,5-diamine, HC Violet No. 2,2-amino-6-chloro-4-nitrophenol, 4-(3-hydroxypropylamino)-3-nitrophenol,HC Yellow No. 13, 6-nitro-1,2,3,4-tetrahydroquinoxaline, HC Red No. 14,HC Yellow No. 15, HC Yellow No. 14,N2-methyl-6-nitropyridine-2,5-diamine,N1-allyl-2-nitrobenzene-1,4-diamine, HC Red No. 8, HC Green No. 1, HCBlue No. 14; Natural dyes such as Annato, Anthocyanin, Beetroot,Carotene, Capsanthin, Lycopene, Chlorophyll, Henna, Indigo, Cochineal;and mixtures thereof.

When the composition is obtained by mixing a fluorophore composition anda developer composition, the direct dyes are usually incorporated intothe fluorophore composition.

Chelants

The composition according to the present invention may further comprisechelants (also known as “chelating agent”, “sequestering agent”, or“sequestrant”) in an amount sufficient to reduce the amount of metalsavailable to interact with formulation components, particularlyoxidizing agents, more particularly peroxides. Chelants are well knownin the art and a non-exhaustive list thereof can be found in A E Martell& R M Smith, Critical Stability Constants, Vol. 1, Plenum Press, NewYork & London (1974) and AE Martell & RD Hancock, Metal Complexes inAqueous Solution, Plenum Press, New York & London (1996), bothincorporated herein by reference.

Typically, the composition may comprise a total amount of chelantsranging from at least about 0.01%, alternatively from about 0.01% toabout 5%, alternatively from about 0.25% to about 3%, alternatively fromabout 0.5% to about 1%, by weight of the total composition.

Suitable chelants include, but are not limited to: carboxylic acids(such as aminocarboxylic acids), phosphonic acids (such asaminophosphonic acids), polyphosphoric acids (such as linearpolyphosphoric acids), their salts thereof, and mixtures thereof. By“salts thereof”, it is meant—in the context of chelants—all saltscomprising the same functional structure as the chelant they arereferring to and including alkali metal salts, alkaline earth salts,ammonium salts, substituted ammonium salts, and mixtures thereof;alternatively sodium salts, potassium salts, ammonium salts, andmixtures thereof; alternatively monoethanolammonium salts,diethanolammonium salts, triethanolammonium salts, and mixtures thereof.Suitable aminocarboxylic acid chelants comprise at least one carboxylicacid moiety (—COOH) and at least one nitrogen atom. Suitableaminocarboxylic acid chelants include, but are not limited to:diethylenetriamine pentaacetic acid (DTPA), ethylenediamine disuccinicacid (EDDS), ethylenediamine diglutaric acid (EDGA),2-hydroxypropylenediamine disuccinic acid (HPDS),glycinamide-N,N′-disuccinic acid (GADS), ethylenediamine-N—N′-diglutaricacid (EDDG), 2-hydroxypropylenediamine-N—N-disuccinic acid (HPDDS),ethylenediaminetetraacetic acid (EDTA), ethylenedicysteic acid (EDC),ethylenediamine-N—N′-bis(ortho-hydroxyphenyl acetic acid) (EDDHA),diaminoalkyldi(sulfosuccinic acids) (DDS),N,N′-bis(2-hydroxybenzyl)ethylenediamine-N,N′-diacetic acid (HBED),their salts thereof, and mixtures thereof. Other suitableaminocarboxylic type chelants include, but are not limited to:iminodiacetic acid derivatives such as N-2-hydroxyethyl N,N diaceticacid or glyceryl imino diacetic acid, iminodiaceticacid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethylN-2-hydroxypropyl-3-sulfonic acid, β-alanine-N,N′-diacetic acid,aspartic acid-N,N′-diacetic acid, aspartic acid-N-monoacetic acid andiminodisuccinic acid chelants, ethanoldiglycine acid, their saltsthereof, their derivatives thereof, and mixtures thereof. Furthersuitable aminocarboxylic type chelants include, but are not limited to:dipicolinic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, theirsalts thereof, their derivatives thereof, and mixtures thereof.

Suitable aminophosphonic acid chelants comprise an aminophosphonic acidmoiety (—PO3H2) or its derivative —PO3R2, wherein R₂ is a C₁ to C₆ alkylor aryl radical and salts thereof. Suitable aminophosphonic acidchelants include, but are not limited to: aminotri-(1-ethylphosphonicacid), ethylene-diaminetetra-(1-ethylphosphonic acid),aminotri-(1-propylphosphonic acid), aminotri-(isopropylphosphonic acid),their salts thereof, and mixtures thereof; alternativelyaminotri-(methylenephosphonic acid),ethylene-diamine-tetra-(methylenephosphonic acid) (EDTMP) anddiethylene-triamine-penta-(methylenephosphonic acid) (DTPMP), theirsalts thereof, their derivatives thereof, and mixtures thereof.

Suitable alternative chelants include, but are not limited to:polyethyleneimines, polyphosphoric acid chelants, etidronic acid,methylglycine diacetic acid, N-(2-hydroxyethyl)iminodiacetic acid,minodisuccinnic acid, N,N-Dicarboxymethyl-L-glutamic acid,N-lauroyl-N,N′,N″-ethylenediamine diacetic acid, their salts thereof,their derivatives thereof, and mixtures thereof.

In a specific embodiment, the composition comprises a chelant selectedfrom the group consisting of diethylenetriamine-N,N′,N″-polyacids,diethylenetriaminepentaacetic acid (DTPA),diethylenetriaminepenta(methylene phosphonic acid) (DTPMP),diamine-N,N′-dipolyacid, monoamine monoamide-N,N′-dipolyacid,ethylenediaminedisuccinic acid (EDDS), their salts thereof, theirderivatives thereof, and mixtures thereof; alternativelyethylenediaminedisuccinic acid (EDDS).

When the composition of the invention is obtained by mixing afluorophore composition and a developer composition, the chelants may beincorporated in the fluorophore composition and/or in the developercomposition. A chelant is usually present in the developer compositionfor stability reason.

Radical Scavengers

According to the present invention, the compositions may comprise aradical scavenger. As used herein the term radical scavenger refers to aspecies that can react with a radical, to convert the radical species bya series of fast reactions to an unreactive or less reactive species.The radical scavenger is also preferably selected such that it is not anidentical species as the alkalising agent and is present in an amountsufficient to reduce the damage to the hair during thecolouring/bleaching process. The compositions of the present inventioncomprise a radical scavenger from about 0.1% to about 10%, preferablyfrom about 1% to about 7% by weight of the radical scavenger relative tothe total weight of the composition.

Suitable radical scavengers for use herein may be selected from theclasses of alkanolamines, amino sugars, amino acids, esters of aminoacids and mixtures thereof. Suitable compounds include3-substituted-pyrazol-5-ones, 3-carboxy-1H-pyrazol-5-one,3-methyl-1-phenyl-pyrazol-5-one, 3-methyl-1-p-tolyl-pyrazol-5-one,3-methyl-1-(4-sulfophenyl)-pyrazol-5-one,3-methyl-1-(4-sulfoamidophenyl)-pyrazol-5-one,3-methyl-1-(3-sulfophenyl)-pyrazol-5-one,3-methyl-1-(3-sulfoamidophenyl)-pyrazol-5-one,3-methyl-1-(2-chloro-5-sulfophenyl)-pyrazol-5-one,3-methyl-1-(2,5-dichloro-4-sulfophenyl)-pyrazol-5-one,3-methyl-1-(4-chlorophenyl)-pyrazol-5-one,3-methyl-1-(4-carboxyphenyl)-pyrazol-5-one,3-carboxy-1-phenyl-pyrazol-5-one,3-carboxy-1-(4-sulfophenyl)-pyrazol-5-one, 1,3-diphenyl-pyrazol-5-one,methyl pyrazol-5-one-3-carboxylate, 3-amino-1-propanol,4-amino-1-butanol, 5-amino-1-pentanol, 1-amino-2-propanol,1-amino-2-butanol, 1-amino-2-pentanol, 1-amino-3-pentanol,1-amino-4-pentanol, 3-amino-2-methylprop an-1-ol,1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, glucosamine,N-acetylglucosamine, glycine, arginine, lysine, proline, glutamine,histidine, sarcosine, serine, glutamic acid, tryptophan, or mixturesthereof, or the salts, such as the potassium, sodium, or ammonium saltsthereof, or mixtures thereof. In some embodiments, the inventivecompositions may comprise glycine, sarcosine, lysine, serine,2-methoxyethylamine, glucosamine, glutamic acid, morpholine, piperidine,ethylamine, 3-amino-1-propanol, or mixtures thereof.

pH Modifiers and Buffering Agents

The composition according to the present invention may further comprise,in addition to the alkalizing agent discussed above, a pH modifierand/or buffering agent in an amount that is sufficiently effective toadjust the pH of the composition to fall within a range from about 3 toabout 13, alternatively from about 8 to about 12, alternatively fromabout 9 to about 11.

Suitable pH modifiers and/or buffering agents include, but are notlimited to: ammonia; alkanolamides (such as monoethanolamine,diethanolamine, triethanolamine, monopropanolamine, dipropanolamine,tripropanolamine, tripropanolamine, 2-amino-2-methyl-1-propanol,2-amino-2-hydroxymethyl-1,3,-propandiol); guanidium salts; alkali metaland ammonium hydroxides and carbonates; and mixtures thereof.

Further pH modifiers and/or buffering agents include, but are notlimited to: sodium hydroxide; ammonium carbonate; acidulents (such asinorganic and inorganic acids including for example phosphoric acid,acetic acid, ascorbic acid, citric acid or tartaric acid, hydrochloricacid); and mixtures thereof.

Thickeners and/or Rheology Modifiers

The composition according to the invention may further comprise athickener in an amount sufficient to provide the composition with aviscosity so that it can be readily applied to the hair without undulydripping off the hair and causing mess.

Typically, the composition may comprise a total amount of thickenersranging from at least about 0.1%, alternatively at least about 1%,alternatively at least about 10%, alternatively at least about 20%, byweight of the total composition.

Suitable thickeners include, but are not limited to: associativepolymers, polysaccharides, non-associative polycarboxylic polymers, andmixtures thereof.

As used herein, the expression “associative polymers” means amphiphilicpolymers comprising both hydrophilic units and hydrophobic units, forexample, at least one C8 to C30 fatty chain and at least one hydrophilicunit. Associative polymers are capable of reversibly combining with eachother or with other molecules. Suitable associative thickeners include,but are not limited to: nonionic amphiphilic polymers comprising atleast one hydrophilic unit and at least one fatty-chain unit; anionicamphiphilic polymers comprising at least one hydrophilic unit and atleast one fatty-chain unit; cationic amphiphilic polymers comprising atleast one hydrophilic unit and at least one fatty-chain unit; andamphoteric amphiphilic polymers comprising at least one hydrophilic unitand at least one fatty-chain unit, and mixtures thereof.

Suitable nonionic amphiphilic polymers comprising at least one fattychain and at least one hydrophilic unit include, but are not limited to:celluloses modified with groups comprising at least one fatty chain(such as hydroxyethylcelluloses modified with groups comprising at leastone fatty chain chosen from alkyl, alkenyl and alkylaryl groups);hydroxypropyl guars modified with groups comprising at least one fattychain; polyether urethanes comprising at least one fatty chain (such asC8-C30 alkyl or alkenyl groups); copolymers of vinylpyrrolidone and offatty-chain hydrophobic monomers; copolymers of C1-C6 alkyl acrylates ormethacrylates and of amphiphilic monomers comprising at least one fattychain; copolymers of hydrophilic acrylates or methacrylates and ofhydrophobic monomers comprising at least one fatty chain, and mixturesthereof. Commercially available anionic materials include those sold asSepigel 305 by Seppic.

Suitable nonionic amphiphilic polymers comprising at least onehydrophilic unit and at least one fatty-chain unit include, but are notlimited to: those polymers comprising at least one fatty-chain allylether unit and at least one hydrophilic unit comprising an ethylenicunsaturated anionic monomeric unit (such as a vinylcarboxylic acid unit,particularly a unit chosen from units derived from acrylic acids,methacrylic acids, and mixtures thereof), wherein the fatty-chain allylether unit corresponds to the monomer of formula (XXX) belowCH2═C(R1)CH2OBnR  (XXX)in which R1 is chosen from H and CH3, B is an ethyleneoxy radical, n ischosen from zero and integers ranging from 1 to 100, R is chosen fromhydrocarbon-based radicals chosen from alkyl, alkenyl, arylalkyl, aryl,alkylaryl and cycloalkyl radicals, comprising from 8 to 30 carbon atoms,and, further, for example, from 10 to 24 carbon atoms and even further,for example, from 12 to 18 carbon atoms.

Suitable anionic amphiphilic polymers include, but are not limited to:those polymers comprising at least one hydrophilic unit of unsaturatedolefinic carboxylic acid type, and at least one hydrophobic unit of thetype such as a (C8-C30) alkyl ester or (C8-C30) oxyethylenated alkylester of an unsaturated carboxylic acid, wherein the hydrophilic unit ofunsaturated olefinic carboxylic acid type corresponds to, for example,the monomer of formula (XXXI) belowCH2═C(R1)COOH  (XXXI)in which R1 is chosen from H, CH3, C2H5 and CH2COOH (i.e. acrylic acid,methacrylic, ethacrylic and itaconic acid units); and wherein thehydrophobic unit of the type such as a (C8-C30) alkyl ester or (C8-C30)oxyethylenated alkyl ester of an unsaturated carboxylic acid correspondsto, for example, the monomer of formula (XXXII) belowCH2═C(R1)COOBnR2  (XXXII)in which R1 is chosen from H, CH3, C2H5 and CH2COOH (i.e. acrylate,methacrylate, ethacrylate and itaconate units), B is an ethyleneoxyradical, n is chosen from zero and integers ranging from 1 to 100, R2 ischosen from C8-C30 alkyl radicals, for example, C12-C22 alkyl radical.Anionic amphiphilic polymers may further be cross-linked. Thecrosslinking agent can be a monomer comprising a group (XXXIII) belowCH2═C<  (XXXIII)with at least one other polymerizable group whose unsaturated bonds arenot conjugated with respect to one another. Mention may be made, forexample, of polyallyl ethers such as polyallylsucrose and polyallylpentaerythritol.

Suitable cationic amphiphilic polymers include, but are not limited to:quaternized cellulose derivatives and polyacrylates comprising aminoside groups. The quaternized cellulose derivatives are, for example,chosen from quaternized celluloses modified with groups comprising atleast one fatty chain, such as alkyl, arylalkyl and alkylaryl groupscomprising at least 8 carbon atoms, and mixtures thereof, quaternizedhydroxyethylcelluloses modified with groups comprising at least onefatty chain, such as alkyl, arylalkyl and alkylaryl groups comprising atleast 8 carbon atoms, and mixtures thereof. The alkyl radicals borne bythe above quaternized celluloses and hydroxyethylcelluloses, forexample, contain from 8 to 30 carbon atoms. The aryl radicals, forexample, are chosen from phenyl, benzyl, naphthyl and anthryl groups.

Suitable amphoteric amphiphilic polymers comprising at least onehydrophilic unit and at least one fatty-chain unit, may be made, forexample, of methacrylamidopropyltrimethylammonium chloride/acrylicacid/C8-C30 alkyl methacrylate copolymers, wherein the alkyl radical is,for example, a stearyl radical.

Preferred associative polymers comprise at least one hydrophilic unitwhich is unsaturated carboxylic acid or its derivatives, and at leastone hydrophobic unit which is a C8 to C30 alkyl ester or oxyethylenatedC8-C30 alkyl ester of unsaturated carboxylic acid. The unsaturatedcarboxylic acid is preferably acrylic acid, methacrylic acid or itaconicacid. Commercially available materials include those sold as Aculyn-22by Rohm & Haas; Permulen TR1, Carbopol 2020, Carbopol Ultrez-21/-30 byNoveon, Structure 2001/3001 by National Starch. Other preferredassociative polymers include polyether polyurethane, commerciallyavailable as Aculyn-44/-46 by Rohm and Haas. Further preferredassociative polymers include cellulose modified with groups comprisingat least one C8-C30 fatty chain, commercially available under the tradename Natrosol Plus Grade 330 CS by Aqualon.

Suitable non-associative cross-linked polycarboxylic polymers include,but are not limited to: cross-linked acrylic acid homopolymers,copolymers of acrylic or (meth)acrylic acid and of C1-C6 alkyl acrylateor (meth)acrylate, and mixtures thereof. Commercially availablematerials include those sold as Carbopol 980/981/954/1382/2984/5984 byNoveon, Synthalen M/Synthalen L/Synthalen K/Synthalen CR by 3V,Aculyn-33 by Rohm and Haas.

Suitable polysaccharides include, but are not limited to: glucans,modified and unmodified starches (such as those derived, for example,from cereals, for instance wheat, corn or rice, from vegetables, forinstance yellow pea, and tubers, for instance potato or cassaya),amylose, amylopectin, glycogen, dextrans, celluloses and derivativesthereof (methylcelluloses, hydroxyalkylcelluloses, ethylhydroxyethylcelluloses, and carboxymethylcelluloses), mannans, xylans,lignins, arabans, galactans, galacturonans, chitin, chitosans,glucuronoxylans, arabinoxylans, xyloglucans, glucomannans, pectic acidsand pectins, alginic acid and alginates, arabinogalactans, carrageenans,agars, glycosaminoglucans, gum arabics, gum tragacanths, ghatti gums,karaya gums, carob gums, galactomannans, such as guar gums, and nonionicderivatives thereof (hydroxypropyl guar) and bio-polysaccharides, suchas xanthan gums, gellan gums, welan gums, scleroglucans, succinoglycans,and mixtures thereof. Suitable polysaccharides are described in“Encyclopedia of Chemical Technology”, Kirk-Othmer, Third Edition, 1982,volume 3, pp. 896-900, and volume 15, pp. 439-458, in “Polymers inNature” by E. A. MacGregor and C. T. Greenwood, published by John Wiley& Sons, Chapter 6, pp. 240-328, 1980, and in “IndustrialGums—Polysaccharides and their Derivatives”, edited by Roy L. Whistler,Second Edition, published by Academic Press Inc., all three beingincorporated herein by reference. A preferred polysaccharide is abio-polysaccharide, particularly bio-polysaccharides selected fromxanthan gum, gellan gum, welan gum, scleroglucan or succinoglycan;commercially available as Keltrol® T by Kelco and Rheozan® by RhodiaChimie. Another preferred polysaccharide is hydroxypropyl starchderivative, particularly hydroxypropyl starch phosphate, commerciallyavailable as Structure XL® by National Starch, a hydrophobicallymodified cellulose derivative, commercially available as Structure® Cel500 HM by AkzoNobel.

Commercially available salt-tolerant thickeners include, but not limitedto: xanthan, guar, hydroxypropyl guar, scleroglucan, methyl cellulose,ethyl cellulose (commercially available as Aquacote), hydroxyethylcellulose (Natrosol), carboxymethyl cellulose, hydroxypropylmethylcellulose, microcrystalline cellulose, hydroxybutylmethyl cellulose,hydroxypropyl cellulose (Klucel), hydroxyethyl ethyl cellulose, cetylhydroxyethyl cellulose (Natrosol Plus 330), polyvinylpyrrolidone(Povidone, FlexiThix™), Acrylates/Ceteth-20 Itaconate Copolymer(Structure 3001), hydroxypropyl starch phosphate (Structure ZEA),polyethoxylated urethanes or polycarbamyl polyglycol ester such asPEG-150/Decyl/SMDI copolymer (Aculyn 44), PEG-150/Stearyl/SMDI copolymer(Aculyn 46), trihydroxystearin (Thixcin), acrylates copolymer (Aculyn33) or hydrophobically modified acrylate copolymers (such asAcrylates/Steareth-20 Methacrylate Copolymer as Aculyn 22),acrylates/steareth-20 methacrylate crosspolymer (Aculyn 88),acrylates/vinyl neodecanoate crosspolymer (Aculyn 38),acrylates/beheneth-25 methacrylate copolymer (Aculyn 28),acrylates/C10-30 alkyl acrylate crosspolymer (Carbopol ETD 2020),non-ionic amphophilic polymers comprising at least one fatty chain andat least one hydrophilic unit selected from polyether urethanescomprising at least one fatty chain, blends of Ceteth—10 phosphate,Dicetyl phosphate and Cetearyl alcohol (available as Crodafos CES), andmixtures thereof.

Carbonate Ion Sources

The composition according to the present invention may further comprisea source of carbonate ions, carbamate ions, hydrogen carbonate ions, andmixtures thereof in a sufficient amount to reduce damage to the hairduring the process.

Typically, the composition may comprise a total amount of a carbonateion source ranging from about 0.1% to about 15%, alternatively fromabout 0.1% to about 10%, alternatively from about 1% to about 7%, byweight of the total composition.

Suitable carbonate ion sources include, but are not limited to: sodiumcarbonate, sodium hydrogen carbonate, potassium carbonate, potassiumhydrogen carbonate, guanidine carbonate, guanidine hydrogen carbonate,lithium carbonate, calcium carbonate, magnesium carbonate, bariumcarbonate, ammonium carbonate, ammonium hydrogen carbonate and mixturesthereof; alternatively sodium hydrogen carbonate, potassium hydrogencarbonate, and mixtures thereof; alternatively ammonium carbonate,ammonium hydrogen carbonate, and mixtures thereof.

Conditioning Agents

The composition according to the present invention may further comprisea conditioning agent, and/or be used in combination with a compositioncomprising a conditioning agent.

Typically, the composition may comprise a total amount of conditioningagents ranging from about 0.05% to about 20%, alternatively from about0.1% to about 15%, alternatively from about 0.2% to about 10%,alternatively from about 0.2% to about 2%, alternatively from about 0.5%to 2%, by weight of the total composition. The conditioning agent may beincluded in a separate pre- and/or post-treatment composition.

Suitable conditioning agents include, but are not limited to: silicones,aminosilicones, fatty alcohols, polymeric resins, polyol carboxylic acidesters, cationic polymers, cationic surfactants, insoluble oils and oilderived materials and mixtures thereof. Additional conditioning agentsinclude mineral oils and other oils such as glycerin and sorbitol.

Particularly useful conditioning materials are cationic polymers.Conditioners of cationic polymer type can be chosen from thosecomprising units of at least one amine group chosen from primary,secondary, tertiary and quaternary amine groups that may either formpart of the main polymer chain, or be borne by a side substituent thatis directly attached to the main polymer chain, described hereinafter.

Suitable silicones include, but are not limited to: polyalkylsiloxaneoils, linear polydimethylsiloxane oils containing trimethylsilyl orhydroxydimethylsiloxane endgroups, polymethylphenylsiloxane,polydimethylphenylsiloxane or polydimethyldiphenylsiloxane oils,silicone resins, organofunctional siloxanes having in their generalstructure one or a number of organofunctional group(s), the same ordifferent, attached directly to the siloxane chain and mixtures thereof.Said organofunctional group(s) may be selected from: polyethyleneoxyand/or polypropyleneoxy groups, (per)fluorinated groups, thiol groups,substituted or unsubstituted amino groups, carboxylate groups,hydroxylated groups, alkoxylated groups, quaternium ammonium groups,amphoteric and betaine groups. The silicone can either be used as a neatfluid or in the form of a pre-formed emulsion. Suitable silicones alsoinclude: silicones containing groups that may be ionized into cationicgroups, for example aminosilicones containing at least 10 repeatingsiloxane (Si(CH₃)₂—O) units within the polymer chain, with eitherterminal, graft, or a mixture of terminal and graft aminofunctionalgroups. Example functional groups are not limited toaminoethylaminopropyl, aminoethylaminoisobutly, aminopropyl. In the caseof graft polymers, the terminal siloxane units can be (CH₃)₃Si—O,R₁₂(CH₃)₂Si—O, where R₁₂ can be either OH or OR₁₃, where R₁₃ is a C1-C8alkyl group, or a mixture of both terminal groups. These silicones arealso available as preformed emulsions. Commercially availableaminosilicones include those sold as DC-2-8566, DC 7224, DC-2-8220 byDow Corning; SF1708, SM2125 by GE Silicones; Wacker Belsil ADM 653/ADM1100/ADM 1600/ADM 652/ADM 6057E/ADM 8020 by Wacker Silicones; DC929,DC939, DC949 by Dow Corning; SM2059 by GE Silicones. Suitableaminosilicones may also contain additional functional groups,particularly additional functional groups including polyoxyalkylene, thereaction product of amines and carbinols, and alky chains. Commerciallyavailable materials are known as methoxy PEG/PPG-7/3 AminopropylDimethicone (e.g. Abil Soft AF100, by Degussa), or as Bis(C13-15Alkoxy)PG Amodimethicone (e.g. DC 8500, by Dow Corning).

Suitable cationic polymers include, but are not limited to: polymerscomprising units of at least one amine group chosen from primary,secondary, tertiary and quaternary amine groups that may either formpart of the main polymer chain or be borne by a side substituent that isdirectly attached to the main polymer chain. Such cationic polymersgenerally have a number average molecular mass ranging from about 500 toabout 5×10⁶, alternatively from about 1000 to about 3×10⁶. Preferablythe cationic polymers are selected from polymers of the polyamine,polyamino amide and polyquaternary ammonium type.

Suitable polymers of the polyamine, polyamino amide and polyquaternaryammonium type include, but are not limited to:

1) Homopolymers and copolymers derived from acrylic or methacrylicesters or amides. Copolymers of these polymers may also comprise atleast one unit derived from comonomers which may be chosen from thefamily of acrylamides, methacrylamides, diacetone acylamides,acrylamides and methacrylicamides substituted on the nitrogen with atleast one group chosen from lower (C1-C4) alkyls, acrylic andmethacrylic acids and esters thereof, vinlylactams such asvinlypyrrolidone and vinylcaprolactam, and vinyl esters. Suitableexamples include copolymers of acrylamide and ofmethacryloyloxyethyltrimethylammonium methosulfate, including polymersknown as Polyquaternium-5 (e.g. commercially available under the tradename Reten 210/220/230/240/1104/1105/1006 by Hercules; Merquat 5/5 SF byNalco); copolymers of vinylpyrrolidone and dimethylaminopropylmethacrylamide, including polymers known as Polyquaternium-28 (e.g.Gafquat HS-100 by ISP); coplolymers of vinyl pyrrolidone anddialkyaminoalkyl acrylates or methactylates, including polymers known asPolquaternium-11 (see Gafquat 440/734/755/755N by ISP; Luviquat PQ11 PMby BASF; Polyquat-11 SL by Sino Lion); copolymers vinylpyrrolidone,dimethylaminopropyl methacrylamide and methacryloylaminopropyllauryldimonium chloride, including polymers known as polyquaternium-55(e.g. Styleze W-20 by ISP); copolymers of acrylic acid, acrylamide andmethacrylamidopropyltrimonium chloride, including polymers known asPolyquaternium-53 (e.g. Merquat 2003 by Nalco); copolymers ofdimethyaminopropylacrylate (DMAPA), acrylic acid and acrylonitrogens anddiethyl sulphate, including polymers known as Polyquaternium-31 (e.g.Hypan QT100 by Lipo); copolymers of acrylamide,acrylamidopropyltrimonium chloride, 2-amidopropylacrylamide sulfonate,and dimethyaminopropylacrylate (DMAPA), including polymers known aspolyquaternium-43 (e.g. Bozequat 4000 by Clairant); copolymers ofacrylic acid, methylacrylate and methacrylamidopropyltrimonium chloride,including polymers known as Polyquaternium-47 (e.g. Merquat 2001/2001Nby Nalco); copolymers of methacryloyl ethyl betaine, 2-hydroxyethylmethacrylate and methacryloyl ethyl trimethyl ammonium chloride,including polymers known as Polyquaternium-48 (e.g. Plascize L-450 byGoo Chemical); copolymers of acrylic acid diallyl dimethyl ammoniumchloride and acrylamide, including polymers known as polyquaternium-39(e.g. Merquat 3330/3331 by Nalco). Further suitable examples includecopolymers of methacrylamide methacrylamido-propyltrimonium andmethacryloylethyltrimethyl ammonium chloride and their derivatives,either homo or copolymerised with other monomers, including polymersknown as Polyquaternium-8, Polyquaternium-9, Polyquaternium-12,Polyquaternium-13 Polyquaternium-14, Polyquaternium-15 (e.g. Rohagit KF720 F by Rohm), Polyquaternium-30 (e.g. Mexomere PX by Chimex),Polyquaternium-33, Polyquaternium-35, Polyquaternium-36 (e.g. Plex 3074L by Rhon), Polyquaternium 45 (e.g. Plex 3073L by Rohn), Polyquaternium49 (e.g. Plascize L-440 by Goo Chemicals), Polyquaternium 50 (e.g.Plascize L-441 by Goo Chemicals), Polyquaternium-52.

2) Cationic polysaccharides, such as cationic celluloses and cationicgalactomannan gums. Among the cationic polysaccharides that maybementioned, for example, are cellulose ether derivatives comprisingquaternary ammonium groups and cationic cellulose copolymers orcellulose derivatives grafted with a water-soluble quaternary ammoniummonomer and cationic galactomannan gums. Suitable examples includecopolymers of hydroxyethylcelluloses and diallyldimethyl ammoniumchlorides, including polymers known as Polyquaternium-4 (e.g. Celquat L200 and Celquat H 100 by National Starch); copolymers ofhydroxyethylcelluloses and a trimethyl ammonium substituted epoxide,including polymers known as Polyquaternium-10 (e.g. AECPolyquaternium-10 by A&E Connock; CatinalC-100/HC-35/HC-100/HC-200/LC-100/LC-200 by Toho; Celquat SC-240C/SC-230Mby National Starch; Dekaquat 400/3000 by Dekker; Leogard GP by AkzoNobel; RITA Polyquat 400/3000 by RITA; UCARE PolymerJR-125/JR-400/JR-30M/LK/LR 400/LR 30M by Amerchol); copolymers ofhydroxyethylcelluloses and lauryl dimethyl ammonium substitutedepoxides, including polymers known as Polyquaternium-24 (e.g. Quatrisoftpolymer LM-200 by Amerchol); derivatives of hydroxypropyl guar,including polymers as guar hydroxypropyltrimonium chloride (e.g. CatinalCG-100, Catinal CG-200 by Toho; Cosmedia Guar C-261N, Cosmedia GuarC-261N, Cosmedia Guar C-261N by Cognis; DiaGum P 5070 by FreedomChemical Diamalt; N-Hance Cationic Guar by Hercules/Aqualon; Hi-Care1000, Jaguar C-17, Jaguar C-2000, Jaguar C-13S, Jaguar C-14S, JaguarExcel by Rhodia; Kiprogum CW, Kiprogum NGK by Nippon Starch);hydroxypropyl derivatives of guar hydroxypropyltrimonium chloride,including polymers known as hydroxypropyl guar hydroxypropyltrimoniumchloride (e.g. Jaguar C-162 by Rhodia).

3) Polyamino amide derivatives resulting from the condensation ofpolyalkylene polyamines with polycarboxylic acids followed by alkylationwith difunctional agents. Among the derivative, mention may be made forexample to adipic acid/dimethylaminohydroxypropyl/diethylenetriamine.

4) Polymers obtained by reaction of a polyalkylene polyamine comprisingtwo primary amines groups and at last one secondary amine group with adecarboxylic acid chosen from diglycolic acids and saturated aliphaticdicarboxylic acids comprising from 3 to 8 carbon atoms. Suitableexamples include the polymer adipic acid/epxoypropyl/diethylenetriamine.

5) Cyclopolymers of dialkdiallylamine or of dialkyldiallyammonium,including: Dimethyldiallyammonium chloride polymers, including polymersknown as Polyquaternium-6 (e.g. Merquat 100 by Nalco; Mirapol 100 byRhodia; Rheocare CC6 by Cosmetic Rheologies; AEC polyquaternium-6 by A&EConnock; Agequat 400 by CPS; Conditioner P6 by 3V Inc.; Flocare C106 bySNF; Genamin PDAC by Clariant; Mackernium 006 by McIntyre); copolymersof acrylamides and dimethyldiallylammonium chlorides monomers, includingpolymers known as Polyquaternium-7 (e.g. AEC Polyquaternium-7 by A&EConnock; Agequat-5008/C-505 by CPS; Conditioner P7 by 3V Inc.; Flocare C107 by SNF; Mackernium 007/007S by McIntyre; ME Polymer 09W by Toho;Merquat 550/2200/S by Nalco; Mirapol 550 by Rhodia; Rheocare CC7/CCP7 byCosmetic Rheologies; Salcare HSP-7/SC10/Super 7 by Ciba); copolymers ofdimethyldiallylammoniumchlorides and acrylic acids, including polymersknown as polyquaternary-22 (e.g. Merquat 280/Merquat 295 by Nalco).

6) Quaternary diammonium polymers comprising repeat units correspondingto [-N+(R1)(R2)-A1−N+(R3)(R4)−B1-][2X-], in which R1, R2, R3 and R4,which may be identical or different, are chosen from aliphatic,alicyclic and arylaliphatic radicals comprising from 1 to 20 carbonatoms and from lower hydroxyalkylaliphatic radicals, or R1, R2, R3 andR4, together or separately, constitute, with the nitrogen atoms to whichthey are attached, heterocycles optionally comprising a secondheteroatom other then nitrogen, or R1, R2, R3 and R4, are chosen fromliner or branched C1-C6 alkyl radicals substituted with at least onegroup chosen from nitrile, ester, acyl and amide groups and groups of—CO—O—R5-D and —CO—NH—R5-D wherein R5 is chosen from alkylene groups andD is chosen from quaternary ammonium groups. A1 and B 1, which may beidentical or different, are chosen from linear and branched, saturatedor unsaturated polymethylene groups comprising 2 to 20 carbon atoms. Thepolymethylene groups may comprise, linked to or intercalated in the mainring, at least one entity chosen from aromatic rings, oxygen and sulphuratoms and sulphoxide, sulphone, disulphide, amino, alkylamino, hydroxyl,quaternary, ammonium, ureido, amide and ester groups, and X— is an anionderived from inorganic and organic acids. D is chosen from a glycolresidue, a bis-secondary diamine residue, a bis-primary diamine residueor a ureylene group. Suitable examples include polymers known asHexadimethrine chloride, where R1, R2, R3 and R4 are each methylradicals, A1 is (CH2)3 and B1 is (CH2)6 and X═Cl; as polyquaternium-34where R1 and R2 are ethyl radicals and R3 and R4 are methyl radicals andA1 is (CH2)3 and B1 is (CH2)3 and X═Br (e.g. Mexomere PAX by Chimax).

7) Polyquaternary ammonium polymers comprising repeating units offormula [-linesN+(R6)(R7)-(CH2)r-NH—CO—(CH2)q-(CO)t-NH—(CH2)s-N+(R8)(R9)-A-][2X-], inwhich R6, R7, R8 and R9 which may be identical or different, are chosenfrom a hydrogen atom and a methyl, ethyl, propyl, hydroxyethyl,hydroxypropyl, and —CH2CH2(OCH2CH2)pOH radicals, wherein p is equal to 0or an integer ranging from 1 to 6, wherein R6, R7, R8 and R9 do not allsimultaneously represent a hydrogen atom. R and s which maybe identicalor different are each an integer ranging from 1 to 6, q is equal to 0 oran integer ranging from 1 to 34 and X− is anion such as a halide. T isan integer chosen to be equal to 0 or 1. A is chosen from divalentradicals such as —CH2-CH2-O—CH2-CH2-. Suitable examples include:polymers known as polyquaternium-2, where r=s=3, q=0, t=0, R6, R7, R8and R9 are methyl groups, and A is —CH2-CH2-O—CH2-CH2 (e.g. Ethpol PQ-2from Ethox; Mirapol A-15 by Rhodia); as polyquaternium-17 where r=s=3,q=4, t=1 R6, R7, R8 and R9 are methyl groups, and A is—CH2-CH2-O—CH2-CH2; as Polyquaternium 18, where r=s=3, q=7, t=1 R6, R7,R8 and R9 are methyl groups, and A is —CH2-CH2-O—CH2-CH2; as the blockcopolymer formed by the reaction of Polyquaternium-2 withPolyquaternium-17, which are known as Polyquaternium 27 (e.g. Mirapol175 by Rhodia).

8) Copolymers of vinylpyrrolidones and of vinylimidazoles and optionallyvinylcaprolactums, including polymers known as Polyquaternary-16 formedfrom methylvinylimidazolium chlorides and vinylpyrrolidones (e.g.Luviquat FC370//FC550/FC905/HM-552 by BASF); copolymers ofvinylcaprolactams and vinylpyrrolidones with methylvinylimidazoliummethosulfates, including polymers known as Polyquaternium-46 (e.g.Luviquat Hold by BASF); copolymers of vinylpyrrolidones and quaternizedimidazolines, including polymers known as polyquaternary 44 (e.g.Luviquat Care by BASF).

9) Polyamines such as Polyquart H sold by Cognis under the referencename polyethylene glycol (15) tallow polyamine.

10) Cross linked methacryloyloxy(C1-C4)alkyltri(C1-C4)alkylammonium saltpolymers such as the polymers obtained by homopolymerisation ofdimethylaminoethyl methacrylates quaternized with methyl chloride, or bycopolymerisation of acrylamides with dimethylaminoethyl methacrylatesquaternized with methyl chloride, the homo or copolymerisation beingfollowed by crosslinking with a compound comprising olefinicunsaturation, such as methylenebisacrylamides, including polymers knownas Polyquaternium-37 (e.g. Synthalen CN/CR/CU sold by 3V sigma; or as adispersion in another media such as Salcare SC95/SC96 by Ciba; RheocareCTH(E) by Cosmetic Rheologies) and polymers known as Polyquaternium-32(e.g. sold as a dispersion in mineral oil such as Salcare SC92 by Ciba).

11) Further examples of cationic polymers include polymers known asPolyquaternium 51 (e.g. Lipidure-PMB by NOF), as Polyquaternium 54 (e.g.Qualty-Hy by Mitsui), as Polyquaternium 56 (e.g. Hairrol UC-4 by Sanyochemicals), as Polyquaternium 87 (e.g. Luviquat sensation by BASF).

12) Silicone polymers comprising cationic groups and/or groups which maybe ionised into cationic groups. Suitable examples include cationicsilicones of the general formula(R10-N+(CH3)2)-R11-(Si(CH3)2-O)x-R11-(N+(CH3)2)-R10), where R10 is analkyl derived from coconut oil, and R11 is (CH2CHOCH2O(CH2)3 and x is anumber between 20 and 2000, including polymers known as Quaternium 80(e.g. Abil Quat 3272/3474 sold by Goldschmidt); silicones containinggroups which may be ionised into cationic groups, for exampleaminosilicones containing at least 10 repeating siloxane —(Si(CH3)2-O)units within the polymer chain, with either terminal, graft or a mixtureof terminal and graft aminofunctional groups. Example functional groupsare not limited to aminoethylaminopropyl, aminoethylaminoisobutly,aminopropyl. In the case of graft polymers, the terminal siloxane unitscan either be (CH3)3Si—O or R12(CH3)2Si—O, where R12 can be either OH orOR13, where R13 is a C1-C8 alky group, or a mixture of both functionalterminal groups. These silicones are also available as preformedemulsions. Polymer with terminal siloxane units of (CH3)3Si—O examplesincludes polymers known as trimethylsilylamodimethicone (e.g. DC-2-8566,DC 7224, DC-2-8220 by Dow Corning; SF1708, SM 2125 GE Silicones; WackerBelsil ADM 653 by Wacker silicones). Further examples include polymerswith terminal siloxane units of (R12O)(CH3)2Si—O where R12 can be eitherOH or OR13, where R13 is a C1-C8 alky group, or a mixture of bothfunctional terminal groups, known as amodimethicone (e.g. Wacker BelsilADM 1100/ADM 1600/ADM 652/ADM 6057E/ADM 8020 by Wacker Silicones; DC929,DC939, DC949 by Dow Corning; SM2059 by GE silicones). Siliconescontaining groups which may be ionised into cationic groups—for examplesilicones containing at least 10 repeating siloxane —(Si(CH3)2-O) unitswithin the polymer chain, with either terminal, graft or a mixture ofterminal and graft aminofunctional groups, together with additionalfunctional groups. Additional functional groups can includepolyoxyalkylene, the reaction product of amines and carbinols, alkychains. For example products known as methoxy PEG/PPG-7/3 AminopropylDimethicone (e.g. Abil Soft AF100 by Degussa). For example productsknown as Bis (C13-15 Alkoxy) PG Amodimethicone (e.g. DC 8500 by DowCorning).

In a preferred embodiment, the cationic polymer is selected from thegroup consisting of polyquaternium 37, polyquaternium 7, polyquaternium22, polyquaternium 87, and mixtures thereof; particularly from the groupconsisting of polyquaternium 37, polyquaternium 22, and mixturesthereof.

Surfactants

The composition according to the present invention may further comprisea surfactant. Suitable surfactants generally have a lipophilic chainlength of from about 8 to about 30 carbon atoms and can be selected fromanionic surfactants, nonionic surfactants, amphoteric surfactants,cationic surfactants, and mixtures thereof.

Typically, the composition may comprise a total amount of surfactantsranging from about 0.01% to about 60%, alternatively from about 0.05% toabout 30%, alternatively from about 0.1% to about 25%, alternativelyfrom about 0.1% to about 20%, by weight of the total composition.

The compositions may comprise a mixture of an anionic surfactant and anamphoteric surfactant with one or more nonionic surfactants. Thecomposition may comprise a total amount of anionic surfactant rangingfrom about 0.01% to about 20%, alternatively from about 0.05% to about15%, alternatively from about 0.1% to about 15%, by weight of the totalcomposition; and a total amount of amphoteric and/or nonioniccomponents, which may range independently from each other from about0.01% to about 15%, alternatively from about 0.05% to about 10%,alternatively from about 0.1% to about 8%, by weight of the totalcomposition.

Suitable anionic surfactants include, but are not limited to: salts(such as alkaline salts, for example, sodium salts, ammonium salts,amine salts, amino alcohol salts and magnesium salts) of the followingcompounds: alkyl sulphates, alkyl ether sulphates, alkylamido ethersulphates, alkylarylpolyether sulphates, monoglyceride sulphates; alkylsulphonates, alkyl phosphates, alkylamide sulphonates, alkylarylsulphonates, α-olefin sulphonates, paraffin sulphonates; alkylsulphosuccinates, alkyl ether sulphosuccinates, alkylamidesulphosuccinates; alkyl sulphosuccinamates; alkyl sulphoacetates; alkylether phosphates; acyl sarcosinates; acyl isethionates; N-acyltaurates;and mixtures thereof. The alkyl or acyl radical of all of these variouscompounds, for example, comprises from 8 to 24 carbon atoms, and thearyl radical, for example, is chosen from phenyl and benzyl groups.Among the anionic surfactants, which can also be used, mention may alsobe made of fatty acid salts such as the salts of oleic, ricinoleic,palmitic and stearic acids, coconut oil acid or hydrogenated coconut oilacid; acyl lactylates in which the acyl radical comprises from 8 to 20carbon atoms. Weakly anionic surfactants can also be used, such asalkyl-D-galactosiduronic acids and their salts, as well aspolyoxyalkylenated (C₆-C₂₄) alkyl ether carboxylic acids,polyoxyalkylenated (C₆-C₂₄) alkylaryl ether carboxylic acids,polyoxyalkylenated (C₆-C₂₄) alkylamido ether carboxylic acids and theirsalts, for example, those comprising from 2 to 50 ethylene oxide groups,and mixtures thereof. Anionic derivatives of polysaccharides, forexample carboxyalkyl ether of alkyl polyglucosides, can be also used.

Nonionic surfactants are compounds that are well known (see, forexample, in this respect “Handbook of Surfactants” by M. R. Porter,published by Blackie & Son (Glasgow and London), 1991, pp. 116-178).Suitable non-ionic surfactants include, but are not limited to:polyethoxylated, polypropoxylated and polyglycerolated fatty acids,alkyl phenols, α-diols and alcohols comprising a fatty chain comprising,for example, from 8 to 18 carbon atoms, it being possible for the numberof ethylene oxide or propylene oxide groups to range, for example, from2 to 200 and for the number of glycerol groups to range, for example,from 2 to 30. Mention may also be made of copolymers of ethylene oxideand of propylene oxide, condensates of ethylene oxide and of propyleneoxide with fatty alcohols; polyethoxylated fatty amides preferablyhaving from 2 to 30 mol of ethylene oxide and their momoethanolamine anddiethanolamine derivatives, polyglycerolated fatty amides, for example,comprising on average from 1 to 5, and such as from 1.5 to 4, glycerolgroups; polyethoxylated fatty amines such as those containing from 2 to30 mol of ethylene oxide; oxyethylenated fatty acid esters of sorbitanhaving from 2 to 30 mol of ethylene oxide; fatty acid esters of sucrose,fatty acid esters of polyethylene glycol, alkylpolyglycosides,N-alkylglucamine derivatives, amine oxides such as (C₁₀-C₁₄)alkylamineoxides or N-acylaminopropylmorpholine oxides.

Suitable amphoteric surfactants include, but are not limited to:aliphatic secondary and tertiary amine derivatives in which thealiphatic radical is chosen from linear and branched chains comprisingfrom 8 to 22 carbon atoms and comprising at least one water-solubleanionic group (for example carboxylate, sulphonate, sulphate, phosphateor phosphonate); mention may also be made of (C₈-C₂₀)alkylbetaines,sulphobetaines, (C₈-C₂₀)alkylamido(C₁-C₆)alkylbetaines or(C₈-C₂₀)alkylamido(C₁-C₆)alkylsulphobetaines. Among the aminederivatives, mention may be made of the products sold as Miranol, asdescribed, for example, in U.S. Pat. Nos. 2,528,378 and 2,781,354 andhaving the structures of: R₂—CON HCH₂CH₂—N⁺(R₃)(R₄)(CH₂COO⁻), (XXXIV) inwhich: R₂ is chosen from alkyl radicals derived from an acid R₂—COOHpresent in hydrolysed coconut oil, and heptyl, nonyl and undecylradicals, R₃ is a β-hydroxyethyl group and R₄ is a carboxymethyl group;and of R₅—CONHCH₂CH₂—N(B)(C) (XXXV) wherein B represents —CH₂CH₂OX′, Crepresents —(CH₂)_(z)—Y′, with z=1 or 2, X′ is chosen from the—CH₂CH₂—COOH group and a hydrogen atom, Y′ is chosen from —COOH and—CH₂—CHOH—SO₃H radicals, R₅ is chosen from alkyl radicals of an acidR₅—COOH present in coconut oil or in hydrolysed linseed oil, alkylradicals, such as C₇, C₉, C₁₁ and C₁₃ alkyl radicals, a C₁₇ alkylradical and its iso form, and unsaturated C₁₇ radical. These compoundsare classified in the CTFA dictionary, 5^(th) edition, 1993, under thenames disodium cocoamphodiacetate, disodium lauroamphodiacetate,disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodiumcocoamphodipropionate, disodium lauroamphodipropionate, disodiumcaprylamphodipropionate, disodium capryloamphodipropionate,lauroamphodipropionic acid, and cocoamphodipropionic acid. Salts ofdiethyl aminopropyl cocoaspartamid can be also used.

Suitable cationic surfactants include, but are not limited to, thequaternary ammonium salts A) to D) as defined hereinafter:

A) Quaternary ammonium salts of general formula (XXXVI) below:

wherein X⁻ is an anion chosen from halides (chloride, bromide andiodide), (C₂-C₆)alkyl sulphates, such as methyl sulphate, phosphates,alkyl and alkylaryl sulphonates, and anions derived from organic acids,such as acetate and lactate, and wherein R₁ to R₄ are as below in i) orii).

i) Radicals R₁ to R₃, which may be identical or different, are chosenfrom linear and branched aliphatic radicals comprising from 1 to 4carbon atoms, and aromatic radicals such as aryl and alkylaryl. Thealiphatic radicals may comprise at least one hetero atom such as oxygen,nitrogen, sulphur and halogens. The aliphatic radicals may be chosenfrom: alkyl, alkoxy and alkylamide radicals. R₄ is chosen from linearand branched alkyl radicals comprising from 16 to 30 carbon atoms. Asuitable cationic surfactant is, for example, a behenyltrimethylammoniumsalt (for example chloride).

ii) Radicals R₁ and R₂, which may be identical or different, are chosenfrom linear and branched aliphatic radicals comprising from 1 to 4carbon atoms, and aromatic radicals such as aryl and alkylaryl. Thealiphatic radicals may comprise at least one hetero atom such as oxygen,nitrogen, sulphur and halogens. The aliphatic radicals may be chosenfrom alkyl, alkoxy, alkylamide and hydroxyalkyl radicals comprising fromabout 1 to 4 carbon atoms. Radicals R₃ and R₄, which may be identical ordifferent, are chosen from linear and branched alkyl radicals comprisingfrom 12 to 30 carbon atoms, the said alkyl radicals comprise at leastone function chosen from ester and amide functions. R₃ and R₄ may bechosen from (C₁₂-C₂₂)alkylamido(C₂-C₆)alkyl and (C₁₂-C₂₂) alkylacetateradicals. A suitable cationic surfactant is, for example, adicetyldimethyl ammonium salt (for example chloride);

B) Quaternary ammonium salts of imidazolinium of formula (XXXVII) below:

in which R₅ is chosen from alkenyl and alkyl radicals comprising from 8to 30 carbon atoms, for example fatty acid derivatives of tallow, R₆ ischosen from a hydrogen atom, C₁-C₄ alkyl radicals and alkenyl and alkylradicals comprising from 8 to 30 carbon atoms, R₇ is chosen from C₁-C₄alkyl radicals, R₈ is chosen from a hydrogen atom and C₁-C₄ alkylradicals, and X⁻ is an anion chosen from halides, phosphates, acetates,lactates, alkyl sulphates, alkyl sulphonates and alkylaryl sulphonates.In one embodiment, R₅ and R₆ are, for example, a mixture of radicalschosen from alkenyl and alkyl radicals comprising from 12 to 21 carbonatoms, such as fatty acid derivatives of tallow, R₇ is methyl and R₈ ishydrogen. Such a product is, for example, Quaternium-27 (CTFA 1997) orQuaternium-83 (CTFA 1997), commercially available as “Rewoquat®”W75/W90/W75PG/W75HPG by Witco.

C) Diquaternary ammonium salts of formula (XXXVIII):

in which R₉ is chosen from aliphatic radicals comprising from about 16to 30 carbon atoms, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄, which may be identicalor different, are chosen from hydrogen and alkyl radicals comprisingfrom 1 to 4 carbon atoms, and X⁻ is an anion chosen from halides,acetates, phosphates, nitrates and methyl sulphates. Such diquaternaryammonium salts, for example, include propanetallowdiammonium dichloride.

D) Quaternary ammonium salts comprising at least one ester function, offormula (XXXIX) below:

in which: R15 is chosen from C1-C6 alkyl radicals and C1-C6 hydroxyalkyland dihydroxyalkyl radicals; R16 is chosen from: a radical R19C(O)—,linear and branched, saturated and unsaturated C1-C22 hydrocarbon-basedradicals R20, and a hydrogen atom, R18 is chosen from: a radicalR21C(O)—, linear and branched, saturated and unsaturated C1-C6hydrocarbon-based radicals R22, and a hydrogen atom, R17, R19 and R21,which may be identical or different, are chosen from linear andbranched, saturated and unsaturated C7-C21 hydrocarbon-based radicals;n, p and r, which may be identical or different, are chosen fromintegers ranging from 2 to 6; y is chosen from integers ranging from 1to 10; x and z, which may be identical or different, are chosen fromintegers ranging from 0 to 10; X− is an anion chosen from simple andcomplex, organic and inorganic anions; with the proviso that the sumx+y+z is from 1 to 15, that when x is 0, then R16 is R20 and that when zis 0, then R18 is R22. In one embodiment, the ammonium salts of formula(XXXX) can be used, in which: R15 is chosen from methyl and ethylradicals, x and y are equal to 1; z is equal to 0 or 1; n, p and r areequal to 2; R16 is chosen from: a radical R19C(O)—, methyl, ethyl andC14-C22 hydrocarbon-based radicals, and a hydrogen atom; R17, R19 andR21, which may be identical or different, are chosen from linear andbranched, saturated and unsaturated C7-C21, hydrocarbon-based radicals;R18 is chosen from: a radical R21C(O)— and a hydrogen atom. Suchcompounds are commercially available as Dehyquart by Cognis, Stepanquatby Stepan, Noxamium by Ceca, and Rewoquat WE 18 by Rewo-Witco.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A method of imparting improved washfastness whentreating the hair fluorescent compounds, the method comprising: a.applying to the hair a fluorescent material composition comprising oneor more fluorescent compounds, the one or more fluorescent compoundseach comprising a fluorescent compound of Formula V, Formula VIII,Formula X, Formula XII, Formula XIV, Formula XVI, Formula XXVI, FormulaXXVII, homologs thereof, the partially or fully protonated formsthereof, or any combination thereof wherein these Formulas and homologsthereof have the following structures:

or a homolog thereof wherein one, two or three of the ethylenyl linkersbonded to the quaternary nitrogen are replaced by a propylenyl linkergroup;

or a homolog thereof wherein one, two, three, or four of the propylenyllinkers bonded to either or both of the quaternary nitrogens arereplaced by an ethylenyl linker group;

or a homolog thereof wherein one or both of the propylenyl linkersbonded to the benzoxazolyl groups are replaced by an ethylenyl linkergroup;

or a homolog thereof wherein the one or both of the propylenyl linkersbonded to the quinolinyl group or the propylenyl linker bonded to thebenzothiazolyl group are replaced by an ethylenyl linker group;

or a homolog thereof wherein one or both of the propylenyl linkersbonded to the oxygen are replaced by an ethylenyl linker group;

or a homolog thereof wherein one, two, or three of the ethylenyl linkersbonded to the quaternary nitrogen are replaced by a propylenyl linkergroup;

or a homolog thereof wherein one or both of the propylenyl linkersbonded to the nitrogen of the indolyl groups are replaced by anethylenyl linker group;

or a homolog thereof wherein one or both of the propylenyl linker bondedto the nitrogen of the benzothiazolyl group and the propylenyl linkerbonded to the nitrogen of the pyridinyl group is replaced by anethylenyl linker group; and, wherein the composition has a pH of fromabout 7 to about 11; wherein the one or more fluorescent compounds enterthe hair shaft after the composition is applied to the hair; and b.rinsing the hair with water; wherein the pH of the hair after rinsing isfrom about 3.5 to about
 6. 2. The method of claim 1, wherein the one ormore fluorescent compounds each comprise two incipient cations.
 3. Themethod of claim 1, wherein the one or more fluorescent compounds eachhas a molecular weight of less than about 1,000 g/mol.
 4. The method ofclaim 1, wherein the hair treatment composition further comprises one ormore oxidative dye precursors.
 5. The method of claim 1, wherein thehair treatment composition further comprises one or more direct dyes. 6.The method of claim 1, wherein the hair treatment composition has a pHof from about 9 to about
 11. 7. The method of claim 1, wherein the hairtreatment composition has a pH of from about 7 to about
 9. 8. The methodof claim 1, wherein the one or more fluorescent compounds is an opticalbrightening compound.
 9. The method of claim 1, wherein an oxidizingagent is applied before or during the application of the hair treatmentcomposition.
 10. The method of claim 9, wherein the oxidizing agent isselected from the group consisting of peroxides, perborates,percarbonates, persulfates, peroxidases and their substrates, laccasesand their substrates, uricases and their substrates, oxidases and theirsubstrates, and combinations thereof.